Alignment facilities for optical dyes

ABSTRACT

Various non-limiting embodiments disclosed herein provide phase-separating polymer systems including a cured polymeric liquid crystal matrix phase and a guest phase including at least one photoactive material where the guest phase separates from the matrix phase during the curing process. Optical elements, including ophthalmic elements and other articles of manufacture including the phase-separating polymer systems are also disclosed. Methods of forming a liquid crystal phase-separating photoactive polymer system are also described.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.10/846,603, filed May 17, 2004 which claims the benefit of U.S.Provisional Application Ser. No. 60/484,100, filed Jul. 1, 2003, whichdisclosures are hereby specifically incorporated by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

REFERENCE TO A SEQUENCE LISTING

Not applicable.

BACKGROUND

Various non-limiting embodiments disclosed herein relate to methods ofmaking alignment facilities for optical dyes connected to at least aportion of an optical substrate. Other non-limiting embodiments relatedto optical elements, such as but not limited to ophthalmic elements,comprising an alignment facility for an optical dye. Still othernon-limiting embodiments relate to alignment facilities for optical dyescomprising coatings or sheets of an at least partially ordered liquidcrystal material.

Liquid crystal molecules, because of their structure, are capable ofbeing ordered or aligned so as to take on a general direction. As usedherein with reference to the order or alignment of a material orstructure, the term “general direction” refers to the predominantarrangement or orientation of the material or structure. Morespecifically, because liquid crystal molecules have rod- or disc-likestructures, a rigid long axis, and strong dipoles, liquid crystalmolecules can be ordered or aligned by interaction with an externalforce or another structure such that the long axis of each of themolecules takes on an orientation that is generally parallel to a commonaxis. For example, if an electric or magnetic field is applied to a cellcontaining a disordered, fluid-mixture of liquid crystal molecules, thelong axis of essentially all of the liquid crystal molecules can beordered in a direction relative to the applied field. Once the field isremoved, however, the molecules will again randomly distributethemselves in fluid-mixture.

It is also possible to align liquid crystal molecules with an orientedsurface. That is, liquid crystal molecules can be applied to a surfacethat has been oriented, for example by rubbing, grooving, orphoto-alignment methods, and subsequently aligned such that the longaxis of each of the liquid crystal molecules takes on an orientationthat is generally parallel to the general direction of orientation ofthe surface.

Aligning a liquid crystal material with an oriented surface as discussedabove generally involves holding the liquid crystal material on theoriented surface at a temperature above the melting point of the liquidcrystal material for some period of time to allow the liquid crystalmolecules to align themselves. Although the time required for alignmentdepends on several factors, generally speaking, the thicker the layer ofthe liquid crystal material applied to the oriented surface, the longerthe time required to fully align the liquid crystal material. Further,for some thick layers of liquid crystal materials, full alignment maynot be achieved.

Photochromic compounds, dichroic compounds, and photochromic-dichroiccompounds may be incorporated into a coating, a substrate or an organicmaterial, for example a polymer coating. When photochromic compounds,dichroic compounds, and photochromic-dichroic compounds undergo a changefrom one state to another, the molecules of the photochromic compound,dichroic compound, or photochromic-dichroic compound may undergo aconformational change from a first conformational state to a secondconformational state. In addition to a change in color and/or polarizingcapability of the compounds, this conformational change may result in achange in the amount of space that the compound occupies. However, forcertain photochromic compounds, dichroic compounds, or compoundsphotochromic-dichroic materials to effectively align and/or transitionfrom one state to another, for example to transition from a clear stateto a colored state, to transition from a colored state to a clear state,to transition from a non-polarized state to a polarized state, and/or totransition from a polarized state to a non-polarized state, thephotochromic compound, dichroic compound, or photochromic-dichroiccompound must be in an chemical environment that is sufficientlyflexible to allow the compound to transition from a first conformationalstate to the second conformational state at a rate that is sufficient toprovide the desired response over an acceptable time frame. Therefore,new polymeric materials are necessary to further develop photochromic,dichroic, and photochromic-dichroic materials and articles.

BRIEF SUMMARY OF THE DISCLOSURE

Various non-limiting embodiments disclosed herein relate to methods ofmaking alignment facilities for an optical dye and alignment facilitiesmade thereby. For example, one non-limiting embodiment provides a methodof making an alignment facility for an optical dye on at least a portionof an ophthalmic substrate, the method comprising forming a first atleast partial coating on at least a portion of the ophthalmic substrate,the first at least partial coating comprising an at least partiallyordered liquid crystal material having at least a first generaldirection; and forming at least one additional at least partial coatingon at least a portion of the first at least partial coating, the atleast one additional at least partial coating comprising an at leastpartially ordered liquid crystal material having at least a secondgeneral direction that is generally parallel to at least the firstgeneral direction.

Other non-limiting embodiments disclosed herein provide for polymersystems comprising at least one photoactive material, for example,photochromic compounds and photochromic-dichroic compounds. According tocertain non-limiting embodiments, these polymer systems may bephase-separating polymer systems. In one embodiment, the presentdisclosure provides for phase-separating polymer systems comprising anat least partially cured matrix phase comprising a polymeric residue ofat least a first liquid crystal monomer, and a guest phase comprising atleast one photoactive material and at least one liquid crystal material.According to these non-limiting embodiments, at least a portion of theguest phase separates from at least a portion of the matrix phase duringthe at least partial curing of the polymeric residue of the at leastfirst liquid crystal monomer. The at least one photoactive material maybe selected from photochromic compounds and photochromic-dichroiccompounds. Examples of the first liquid crystal monomers and liquidcrystal materials are described in detail herein.

Another non-limiting embodiment of the present disclosure provides foroptical elements. According to these non-limiting embodiments, theoptical elements comprise a substrate and an at least partial layer onat least a portion of a surface of the substrate, where the layercomprises a liquid crystal phase-separated system. The liquid crystalphase-separated system comprises an at least partially cured matrixphase comprising a polymeric residue of at least a first liquid crystalmonomer, and a guest phase comprising at least one photoactive materialand at least one liquid crystal material. According to thesenon-limiting embodiments, the photoactive material is selected fromphotochromic compounds, dichroic compounds, and photochromic-dichroiccompounds. At least one of the first liquid crystal monomer of thematrix phase and the at least one liquid crystal material of the guestphase comprises a mesogen containing compound having a structurerepresented by Formula I:

where P, L, X, Mesogen-1, “w”, and “z” are as described herein.According to these non-limiting embodiments, at least a portion of theguest phase separates from at least a portion of the matrix phase duringthe at least partial curing of the polymeric residue of at least thefirst liquid crystal monomer.

Further non-limiting embodiments of the present disclosure providearticles of manufacture. According to these non-limiting embodiments,the articles of manufacture comprise an at least partially cured matrixphase comprising a polymeric residue of at least a first liquid crystalmonomer, and a guest phase comprising at least one photoactive materialand at least one second liquid crystal monomer or residue thereof.According to these non-limiting embodiments, the photoactive material isselected from photochromic compounds and photochromic-dichroiccompounds. At least one of the first liquid crystal monomer of thematrix phase and the at least one second liquid crystal monomer of theguest phase comprises at least one mesogen containing compound having astructure represented by Formula I, where P, L, X, Mesogen-1, “w”, and“z” are as described herein. According to these non-limitingembodiments, at least a portion of the guest phase separates from atleast a portion of the matrix phase during the at least partial curingof the polymeric residue of at least the first liquid crystal monomer.

Still other non-limiting embodiments of the present disclosure providemethods for forming liquid crystal phase-separating photochromic,dichroic, or photochromic-dichroic polymer systems. According tospecific non-limiting embodiments, the method comprising providing aphase-separating polymer forming composition comprising a matrix phaseforming material comprising at least a first liquid crystal monomer, aguest phase forming material comprising at least one liquid crystalmaterial, and at least one photoactive material selected fromphotochromic compounds or photochromic-dichroic compounds; at leastpartially ordering at least a portion of the at least first liquidcrystal monomer of the matrix phase forming material and at least aportion of the at least one liquid crystal material of the guest phaseforming material such that the at least partially ordered portion of theat least first liquid crystal monomer of the matrix phase formingmaterial has a first general direction and the at least partiallyordered portion of the at least one liquid crystal material of the guestphase forming material has a second general direction that is generallyparallel to the first general direction; causing at least a portion ofthe guest phase forming material to separate from at least a portion ofthe matrix phase forming material by polymerization inducedphase-separation or solvent induced phase-separation, wherein the atleast one photoactive material selectively concentrates in the guestphase forming material; and at least partially curing at least a portionof the matrix phase forming material to produce an at least partiallycured matrix phase.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

Various non-limiting embodiments disclosed herein will be betterunderstood when read in conjunction with the drawings, in which:

FIG. 1 is a schematic, cross-sectional view of an overmolding assemblyaccording to one non-limiting embodiment disclosed herein;

FIGS. 2 and 3 are schematic, cross-sectional views of an optical elementaccording to various non-limiting embodiments disclosed herein; and

FIG. 4 is a schematic, top-plane view of an alignment facility accordingto one non-limiting embodiment disclosed herein.

DETAILED DESCRIPTION

As used in this specification and the appended claims, the articles “a,”“an,” and “the” include plural referents unless expressly andunequivocally limited to one referent.

Additionally, for the purposes of this specification, unless otherwiseindicated, all numbers expressing quantities of ingredients, reactionconditions, and other properties or parameters used in the specificationare to be understood as being modified in all instances by the term“about.” Accordingly, unless otherwise indicated, it should beunderstood that the numerical parameters set forth in the followingspecification and attached claims are approximations. At the very least,and not as an attempt to limit the application of the doctrine ofequivalents to the scope of the claims, numerical parameters should beread in light of the number of reported significant digits and theapplication of ordinary rounding techniques.

Further, while the numerical ranges and parameters setting forth thebroad scope of the invention are approximations as discussed above, thenumerical values set forth in the Examples section are reported asprecisely as possible. It should be understood, however, that suchnumerical values inherently contain certain errors resulting from themeasurement equipment and/or measurement technique.

In the present disclosure and the appended claims, it should beappreciated that where listings of possible structural features, suchas, for example substituent groups, are provided herein using headingsor subheadings, such as, for example: (a), (b) . . . ; (1), (2) . . . ;(i), (ii) . . . ; etc., these headings or subheadings are provided onlyfor convenience of reading and are not intended to limit or indicate anypreference for a particular structural feature or substituent.

The present disclosure describes several different features and aspectsof the invention with reference to various exemplary embodiments. It isunderstood, however, that the invention embraces numerous alternativeembodiments, which may be accomplished by combining any of the differentfeatures, aspects, and embodiments described herein in any combinationthat one of ordinary skill in the art would find useful.

Various non-limiting embodiments disclosed herein are directed towardmethods of making alignment facilities for optical dyes using one ormore liquid crystal materials. As used herein the term “optical dye”means a dye that can affect one or more optical properties of an objectto which it is connected. For example, although not limiting herein, anoptical dye can affect one or more of the color, polarization,UV-absorption, and emission (e.g., fluorescence and phosphorescence)properties of the coating or substrate to which it is connected. Opticaldyes that are useful in conjunction with the various non-limitingembodiments disclosed herein include a wide variety of organic dyes,inorganic dyes, and mixtures thereof. Non-limiting examples of opticaldyes include fixed-tint dyes, as well as dichroic and/or photochromicdyes.

As used herein the term “alignment facility” means a structure that canfacilitate the positioning of one or more other structures or materialsthat are exposed, directly or indirectly, to at least a portion of thefacility. Thus, the alignment facilities according to variousnon-limiting embodiments disclosed herein can be used to facilitate thepositioning of an optical dye. More specifically, the optical dye can bealigned by direct and/or indirect interaction with the alignmentfacility. As used herein the term “align” means bring into suitablearrangement or position by interaction with another material, compoundor structure. For example, although not limiting herein, the alignmentfacilities according to various non-limiting embodiments disclosedherein can directly facilitate the positioning of an optical dye that isin direct contact with the alignment facility. Alternatively, thealignment facility can indirectly facilitate the positioning of anoptical dye by facilitating the positioning of another structure ormaterial, for example and without limitation, a coating of a liquidcrystal material with which the optical dye is in contact.

While not limiting herein, the alignment facilities according to variousnon-limiting embodiments disclosed herein can directly and/or indirectlyfacilitate the positioning of an optical dye that is opticallyanisotropic. As used herein the term “anisotropic” means having at leastone property that differs in value when measured in at least onedifferent direction. Thus, optically anisotropic dyes have at least oneoptical property that differs in value when measured in at least onedifferent direction. One non-limiting example of an opticallyanisotropic dye is a dichroic dye. As used herein the term “dichroic”means capable absorbing one of two orthogonal plane polarized componentsof at least transmitted radiation more strongly than the other. As usedherein, the terms “linearly polarize” or “linearly polarization” mean toconfine the vibrations of the electromagnetic vector of light waves toone direction. Accordingly, dichroic dyes are capable of absorbing oneof two orthogonal plane polarized components of transmitted radiationmore strongly than the other, thereby resulting in linear polarizationof the transmitted radiation. However, while dichroic dyes are capableof preferentially absorbing one of two orthogonal plane polarizedcomponents of transmitted radiation, if the molecules of the dichroicdye are not aligned, no net linear polarization of transmitted radiationwill be achieved. That is, due to the random positioning of themolecules of the dichroic dye, selective absorption by the individualmolecules can cancel each other such that no net or overall linearpolarizing effect is achieved. Thus, it is generally necessary to alignthe molecules of the dichroic dye in order to achieve a net linearpolarization. The alignment facilities according to various non-limitingembodiments disclosed herein can be used to facilitate the positioningof an optically anisotropic dye, such as a dichroic dye, therebyachieving a desired optical property or effect.

Further, various non-limiting embodiments disclosed herein providemethods of making an alignment facility for an optical dye on at least aportion of an optical substrate, such as, but not limited to, anophthalmic substrate. As used herein the term “optical” means pertainingto or associated with light and/or vision. As used herein the term“ophthalmic” means pertaining to or associated with the eye and vision.Non-limiting examples of optical substrates that can be used inconjunction with various non-limiting embodiments disclosed hereininclude ophthalmic substrates, and substrates for use in opticalelements and devices. Examples of optical elements and devices include,but are not limited to, ophthalmic optical displays, windows, andmirrors. As used herein the term “display” means the visible ormachine-readable representation of information in words, numbers,symbols, designs or drawings. As used herein the term “window” means anaperture adapted to permit the transmission of radiation therethrough.Non-limiting examples of windows include automotive and aircrafttransparencies, filters, shutters, and optical switches. As used hereinthe term “mirror” means a surface that specularly reflects a largefraction of incident light.

Non-limiting examples of ophthalmic elements include corrective andnon-corrective lenses, including single vision or multi-vision lenses,which may be either segmented or non-segmented multi-vision lenses (suchas, but not limited to, bifocal lenses, trifocal lenses and progressivelenses), as well as other elements used to correct, protect, or enhance(cosmetically or otherwise) vision, including without limitation,contact lenses, intra-ocular lenses, magnifying lenses, and protectivelenses or visors. Further non-limiting examples of ophthalmic substratesinclude lenses, partially formed lenses, and lens blanks.

Non-limiting examples of organic materials suitable for use in formingophthalmic substrates according to various non-limiting embodimentsdisclosed herein include, but are not limited to, the art-recognizedpolymers that are useful as ophthalmic substrates, e.g., organic opticalresins that are used to prepare optically clear castings for opticalapplications, such as ophthalmic lenses. Specific, non-limiting examplesof organic materials that may be used to form the ophthalmic substratesdisclosed herein include polymeric materials, for examples, homopolymersand copolymers, prepared from the monomers and mixtures of monomersdisclosed in U.S. Pat. No. 5,962,617 and in U.S. Pat. No. 5,658,501 fromcolumn 15, line 28 to column 16, line 17, the disclosures of which U.S.patents are specifically incorporated herein by reference. For example,such polymeric materials can be thermoplastic or thermoset polymericmaterials, can be transparent or optically clear, and can have anyrefractive index required. Non-limiting examples of such disclosedmonomers and polymers include: polyol(allyl carbonate) monomers, e.g.,allyl diglycol carbonates such as diethylene glycol bis(allylcarbonate), which monomer is sold under the trademark CR-39 by PPGIndustries, Inc.; polyurea-polyurethane (polyurea urethane) polymers,which are prepared, for example, by the reaction of a polyurethaneprepolymer and a diamine curing agent, a composition of one such polymerbeing sold under the trademark TRIVEX by PPG Industries, Inc.;polyol(meth)acryloyl terminated carbonate monomer; diethylene glycoldimethacrylate monomers; ethoxylated phenol methacrylate monomers;diisopropenyl benzene monomers; ethoxylated trimethylol propanetriacrylate monomers; ethylene glycol bismethacrylate monomers;poly(ethylene glycol) bismethacrylate monomers; urethane acrylatemonomers; poly(ethoxylated bisphenol A dimethacrylate); poly(vinylacetate); poly(vinyl alcohol); poly(vinyl chloride); poly(vinylidenechloride); polyethylene; polypropylene; polyurethanes;polythiourethanes; thermoplastic polycarbonates, such as thecarbonate-linked resin derived from bisphenol A and phosgene, one suchmaterial being sold under the trademark LEXAN; polyesters, such as thematerial sold under the trademark MYLAR; poly(ethylene terephthalate);polyvinyl butyral; poly(methyl methacrylate), such as the material soldunder the trademark PLEXIGLAS, and polymers prepared by reactingpolyfunctional isocyanates with polythiols or polyepisulfide monomers,either homopolymerized or co- and/or terpolymerized with polythiols,polyisocyanates, polyisothiocyanates and optionally ethylenicallyunsaturated monomers or halogenated aromatic-containing vinyl monomers.Also contemplated are copolymers of such monomers and blends of thedescribed polymers and copolymers with other polymers, for example, toform block copolymers or interpenetrating polymer network products.

Still further, the substrates according to various non-limitingembodiments disclosed herein can be untinted, tinted, linearlypolarizing, photochromic, or tinted-photochromic substrates. As usedherein with reference to substrates the term “untinted” means substratesthat are essentially free of coloring agent additions (such as, but notlimited to, conventional dyes) and have an absorption spectrum forvisible radiation that does not vary significantly in response toactinic radiation. Further, as used herein with reference to substrates,the term “tinted” means substrates that have a coloring agent addition(such as, but not limited to, conventional dyes) and an absorptionspectrum for visible radiation that does not vary significantly inresponse to actinic radiation. As used herein the term “linearlypolarizing” with reference to substrates refers to substrates that areadapted to linearly polarize radiation.

As used herein with the term “photochromic” with reference to compoundsand substrates refers to compounds and substrates having an absorptionspectrum for visible radiation that varies in response to at leastactinic radiation. As used herein the term “actinic radiation” meanselectromagnetic radiation that is capable of causing a response. Actinicradiation includes, for example and without limitation, visible andultraviolet radiation. Further, as used herein with reference tosubstrates, the term “tinted-photochromic” means substrates containing acoloring agent addition as well as a photochromic material, and havingan absorption spectrum for visible radiation that varies in response toat least actinic radiation. Thus for example, in one non-limitingembodiment, the tinted-photochromic substrate can have a first colorcharacteristic of the coloring agent and a second color characteristicof the combination of the coloring agent the photochromic material whenexposed to actinic radiation. Photochromic-dichroic dyes and compoundsmay also be used in specific embodiments herein. As used herein, theterm “photochromic-dichroic” includes materials that possess bothphotochromic properties (i.e., having an absorption spectrum for visibleradiation that varies in response to at least actinic radiation) anddichroic properties (i.e., capable of absorbing one of two orthogonalplane polarized components of at least transmitted radiation morestrongly than the other).

Various non-limiting embodiments of methods of making alignmentfacilities for optical dyes will now be described. One non-limitingembodiment provides a method of making an alignment facility for anoptical dye on at least a portion of an ophthalmic substrate, the methodcomprising forming a first at least partial coating comprising an atleast partially ordered liquid crystal material having at least a firstgeneral direction on at least a portion of the ophthalmic substrate, andthereafter forming at least one additional at least partial coatingcomprising an at least partially ordered liquid crystal material on atleast a portion of the first at least partial coating. Further,according to this non-limiting embodiment, the at least partiallyordered portion of the liquid crystal material of the at least oneadditional at least partial coating can have at least a second generaldirection that is generally parallel to the first general direction ofthe first at least partial coating. As previously discussed, as usedherein with reference to order or alignment of a material or structure,the term “general direction” refers to the predominant arrangement ororientation of the material, compound or structure. Further, it will beappreciated by those skilled in the art that a material or a structurecan have a general direction even though there is some variation withinthe arrangement of the material or structure, provided that the materialor structure has at least one predominate arrangement. Further, as usedherein with reference to the general direction of the liquid crystalmaterials, the terms “first” and “second” are not intended as ordinalnumbers or to indicate a chorological order, but instead are used forclarity in referring to various general directions herein.

As discussed above, according to various non-limiting embodimentsdisclosed herein, the at least partially ordered liquid crystal materialof the first at least partial coating can have at least a first generaldirection. That is, the at least partially ordered liquid crystalmaterial can have one predominate direction throughout the material, orit can have different regions having different general directions. Forexample, the at least partially ordered liquid crystal material of thefirst at least partial coating can have a first region having a firstgeneral direction, and a second region adjacent the first region havinga second general direction that is different from the first generaldirection. Further, the at least partially ordered liquid crystalmaterial of the first at least partial coating can have a plurality ofregions, wherein each region has a general direction that is the same ordifferent from the remaining regions and that together form a pattern ordesign. As discussed herein below in more detail, the at least oneadditional at least partial coating can also have a plurality of regionshaving general directions that are generally parallel to the generaldirections of the first at least partial coating and that together formessentially the same pattern or design as that of the first at leastpartial coating.

As used herein the term “coating” means a supported film derived from aflowable composition, which may or may not have a uniform thickness.Further, as used herein the term coating specifically excludes polymericsheets. As used herein the term “sheet” means a pre-formed film having agenerally uniform thickness and capable of self-support. As used hereinthe term “on” means directly connected to an object (such as, but notlimited to, a substrate or a coating) or indirectly connected to anobject through one or more other coatings, sheets or other structures.

More specifically, according to various non-limiting embodiments,forming the first at least partial coating can comprise applying aliquid crystal material on at least a portion of the ophthalmicsubstrate, at least partially ordering at least a portion of the liquidcrystal material such that the at least partially ordered portion of theliquid crystal material has at least a first general direction, and atleast partially setting at least a portion of the at least partiallyordered liquid crystal material.

Suitable methods of applying liquid crystal materials to at least aportion of a substrate according to various non-limiting embodimentsdisclosed herein include, without limitation: spin coating, spraycoating, spray and spin coating, curtain coating, flow coating, dipcoating, injection molding, casting, roll coating, wire coating,overlaying, and combinations thereof. For example, although not limitingherein, in one specific non-limiting embodiment, liquid crystal materialof the first at least partial coating can be applied to at least aportion of the ophthalmic substrate by spin coating, and thereafter atleast partially ordered.

As used herein the term “order” means bring into a suitable arrangementor position, such as by aligning with another structure or material, orby some other force or effect. Thus, as used herein the term “order”encompasses both contact methods of ordering a material, such asaligning with another structure or material, and non-contact methods ofordering a material, such as by exposure to an external force or effect.The term “order” also encompasses combinations of contact andnon-contact methods.

Non-limiting examples of methods of at least partially ordering liquidcrystal materials according to various non-limiting embodimentsdisclosed herein include exposing the at least a portion of the liquidcrystal material to at least one of: a magnetic field, an electricfield, linearly polarized infrared radiation, linearly polarizedultraviolet radiation, linearly polarized visible radiation and a shearforce. In addition to the aforementioned methods of at least partiallyordering a liquid crystal material, as discussed in more detail below,the liquid crystal materials according to various non-limitingembodiments disclosed herein can be at least partially ordered byaligning the at least a portion of the liquid crystal material withanother material or structure, such as an orientation facility.

In one non-limiting embodiment, the liquid crystal material of the firstat least partial coating is at least partially ordered by exposing atleast a portion of the liquid crystal material to a shear force. Forexample, although not limiting herein, according to this non-limitingembodiment an optical or ophthalmic substrate with the liquid crystalmaterial on at least a portion of its surface can be placed in acentrifuge and the centrifuge can be rotated such that the substratetraverses the perimeter of the centrifuge and that the liquid crystalmaterial flows relative to the surface of the substrate.

Additionally, according to various non-limiting embodiments disclosedherein, at least partially ordering at least a portion of the liquidcrystal material of the first at least partial coating can occur atessentially the same time as applying the liquid crystal material to atleast portion of the substrate, or it can occur after applying theliquid crystal material to the substrate. For example, in onenon-limiting embodiment wherein applying the liquid crystal material andat least partially ordering at least a portion of the liquid crystalmaterial occur at essentially the same time, the liquid crystal materialcan be applied to at least a portion of at least one surface of theophthalmic substrate using an application technique that can introduce ashear force to at least a portion of the liquid crystal material,thereby ordering the long axis of the molecules of the liquid crystalmaterial in a general direction that is generally parallel to thedirection of the shear force during application. For example, althoughnot limiting herein, the liquid crystal material of the first at leastpartial coating can be curtain coated onto at least a portion of atleast one surface of the ophthalmic substrate such that a shear forceare introduced to the liquid crystal material due to the relativemovement of the surface of the ophthalmic substrate with respect to theliquid crystal material being applied. The shear force can cause atleast a portion of the molecules of the liquid crystal material to beordered such that the long axis of the liquid crystal molecules have ageneral direction that is generally parallel to the direction of themovement of the ophthalmic substrate.

In another non-limiting embodiment wherein applying the liquid crystalmaterial of the first at least partial coating occurs before at leastpartially ordering at least a portion of the liquid crystal material,the liquid crystal material can be applied, for example, by spincoating, and, thereafter, the liquid crystal material can be at leastpartially ordered. For example the liquid crystal material can be atleast partially ordered by exposing at least a portion of the liquidcrystal material to a magnetic field, an electric field, linearlypolarized infrared radiation, linearly polarized ultraviolet radiation,linearly polarized visible radiation and/or a shear force. Additionallyor alternatively, at least a portion of the liquid crystal material canbe at least partially ordered by alignment with at least a portion of anorientation facility, as discussed in more detail herein below.

As discussed above, after at least a portion of the liquid crystalmaterial of the first at least partial coating is at least partiallyordered, the at least partially ordered liquid crystal material is atleast partially set. As used herein the term “set” means to fix theliquid crystal material in a desired orientation. Non-limiting examplesof methods of at least partially setting liquid crystal materialsinclude at least partially drying a solvent from the liquid crystalmaterial, and at least partially curing the liquid crystal material, forexample by at least partially cross-linking the liquid crystal materialand/or at least partially polymerizing the liquid crystal material.Non-limiting methods of at least partially polymerizing a liquid crystalmaterial include photo-induced polymerization, thermally-inducedpolymerization, and combinations thereof. Further, photo-inducedpolymerization includes, but is not limited to, polymerization inducedby ultraviolet light, polymerization induced by visible light, andcombinations thereof.

Generally the thickness of the first at least partial coating can be anythickness necessary to achieve the total desired thickness of thealignment facility when added together with the thickness of theadditional at least partial coating(s), which are described below inmore detail. For example and without limitation, according to variousnon-limiting embodiments, the first at least partial coating can have athickness ranging from: 0.5 to 20 microns, 0.5 to 10 microns, and 2 to 8microns. Further, although not limiting herein, according to certainnon-limiting embodiments, the thickness of the first at least partialcoating can be less than that of the at least one additional at leastpartial coating.

As discussed above, according to various non-limiting embodimentsdisclosed herein, after forming the first at least partial coating, atleast one additional at least partial coating comprising a liquidcrystal material is formed on at least a portion of the first at leastpartial coating. More particularly, according to various non-limitingembodiments disclosed herein, forming the at least one additional atleast partial coating can comprise applying a liquid crystal material toat least a portion of the first at least partial coating; at leastpartially ordering at least a portion of the liquid crystal materialsuch that the at least partially ordered portion of the liquid crystalmaterial has at least a second general direction that is generallyparallel to at least the first general direction of the liquid crystalmaterial of the first at least partial coating; and at least partiallysetting at least a portion of the liquid crystal material. Non-limitingmethods of applying and at least partially setting the liquid crystalmaterial of the at least one additional at least partial coating are setforth above in detail with respect to the first at least partialcoating.

As previously discussed, liquid crystal materials are generally capableof being aligned with one or more other structures or materials suchthat the long axis of the molecules of the liquid crystal material takeon a general direction that is generally parallel to the generaldirection of the structure with which the molecules are aligned. Morespecifically, although not limiting herein, according to variousnon-limiting embodiments disclosed herein, the liquid crystal materialof the at least one additional at least partial coating can be at leastpartially ordered by aligning at least a portion of the liquid crystalmaterial with at least a portion of the at least partially orderedliquid crystal material of the first at least partial coating such thatthe long axis of the molecules of the liquid crystal material of the atleast one additional at least partial coating are generally parallel toat least the first general direction of the at least partially orderedliquid crystal material of the first at least partial coating. Thus, inthis manner, the general direction of the liquid crystal material of thefirst at least partial coating can be transferred to the liquid crystalmaterial of the at least one additional at least partially coating.Further, if the liquid crystal material of the first at least partialcoating comprises a plurality of regions having general directions thattogether form a design or pattern (as previously described), that designor pattern can be transferred to the liquid crystal material of the atleast one additional at least partial coating by aligning the liquidcrystal material of the at least one additional at least partial coatingwith liquid crystal material of the first at least partial coating.Additionally, although not required, according to various non-limitingembodiments disclosed herein the at least one additional at leastpartial coating can be exposed to at least one of: a magnetic field, anelectric field, linearly polarized infrared radiation, linearlypolarized ultraviolet radiation, and linearly polarized visibleradiation while being at least partially aligned with at least a portionof the liquid crystal material of the first at least partial coating.

As discussed above with respect to the first at least partial coating,according to various non-limiting embodiments, the at least oneadditional at least partial coating can have any thickness necessary toachieve the desired overall thickness of the alignment facility. Thus,for example and without limitation, according to various non-limitingembodiments disclosed herein, the at least one additional at leastpartial coating can have a thickness ranging from 1 micron to 25microns, and can further have a thickness ranging from 5 microns to 20microns. According to still another non-limiting embodiment, at leastone additional at least partial coating can have a thickness greaterthan 6 microns, and can further have a thickness of at least 10 microns.

As previously discussed, the time required to fully align thick layer ofa liquid crystal material with an oriented surface can be substantial.Further, in some instances, only a portion of the liquid crystalmaterial immediately adjacent oriented surface may be aligned. Thus,according to various non-limiting embodiments wherein thicker alignmentfacilities are desired, the alignment facilities can comprise aplurality of additional at least partial coatings, each having anindependently selected thickness that, when added together with thethickness of the first at least partial coating, form an alignmentfacility having the desired overall thickness. More specifically,according to various non-limiting embodiments disclosed herein, themethod of forming the alignment facility can comprise forming a first atleast partial coating comprising a liquid crystal material (aspreviously described), and thereafter successively forming a pluralityof additional at least partial coatings. That is, after forming thefirst at least partial coating, a plurality of additional at leastpartial coatings can be formed by successively applying a liquid crystalmaterial to at least a portion of a preceding coating, at leastpartially ordering at least a portion of the liquid crystal materialsuch that the at least partially ordered portion of the liquid crystalmaterial has at least one general direction that is generally parallelto a general direction of the preceding coating, and at least partiallysetting at least a portion of the liquid crystal material. Further, eachof the at least partial coatings can have an independently selectedthickness. For example and without limitation, each of the additional atleast partial coatings can have a thickness ranging from 1 micron to 25microns, and can further have a thickness ranging from 5 microns to 20microns. According to another non-limiting embodiment, each of theadditional at least partial coatings can have a thickness greater than 6microns, and can further have a thickness of at least 10 microns.

According to one non-limiting embodiment, forming a plurality ofadditional at least partial coatings can comprise successively formingat least two additional at least partial coatings. In anothernon-limiting embodiment, forming a plurality of additional at leastpartial coatings can comprises successively forming at least threeadditional at least partial coatings. Although according to thesenon-limiting embodiments each of the plurality of additional at leastpartial coatings is formed in succession, according to variousnon-limiting embodiments, the time required to successively form theplurality of coatings can be less than the time required to apply andalign a single coating of the same liquid crystal material having thesame thickness as the plurality of coatings.

Further, as discussed above, it is possible to ‘transfer’ a generaldirection (or plurality of general directions that can together form apattern or design) from one coating to the next by at least partiallyaligning each successive coating with at least a portion of theimmediately preceding coating. For example, although not limitingherein, if the first at least partial coating comprises a plurality ofregions having a plurality of general directions that together form adesign, that design can be transferred to the at least one additionalcoating by alignment of the at least one additional at least partialcoating with the first at least partial coating as discussed above.Further, where the alignment facility comprises a plurality ofadditional at least partial coatings, the design can be transferred toeach of the additional at least partial coatings by successivelyaligning each coating with the preceding coating.

As previously discussed, the thickness of the first at least partialcoating and the thickness and number of additional at least partialcoatings, can be chosen so as to achieve the desired overall thicknessof the alignment facility. Although not limiting herein, according toone non-limiting embodiment, the sum of the thickness of the first atleast partial coating and the thickness of the at least one additionalat least partial coating can range from 10 microns to 50 microns.According to another non-limiting embodiment, the sum of the thicknessof the first at least partial coating and the at least one additional atleast partial coating can range from 20 microns to 40 microns. Accordingto still another non-limiting embodiment, this sum can be greater than20 microns, and further can be at least 22 microns.

Another non-limiting embodiment provides a method of making an alignmentfacility for an optical dye on at least a portion of an opticalsubstrate, the method comprising forming a first at least partialcoating comprising an at least partially ordered liquid crystal materialhaving at least a first general direction on at least a portion of theoptical substrate, and forming at least one additional at least partialcoating comprising an at least partially ordered liquid crystal materialhaving at least a second general direction that is generally parallel toat least the first general direction of the liquid crystal material ofthe first at least partial coating on at least a portion of the first atleast partial coating; wherein a sum of a thickness of the first atleast partial coating and a thickness of the at least one additional atleast partial coating is greater than 20 microns.

Still another non-limiting embodiment provides a method of making analignment facility for an optical dye on at least a portion of anoptical substrate, the method comprising forming an at least partialcoating comprising an at least partially ordered liquid crystal materialhaving at least a first general direction on at least a portion of theoptical substrate, the at least partial coating having a thickness of atleast 6 microns. According to this non-limiting embodiment, forming theat least partial coating can comprise applying a liquid crystal materialto at least a portion of the optical substrate such that the liquidcrystal material has a thickness of greater than 6 microns, at leastpartially ordering at least a portion of the liquid crystal materialsuch that at least a portion of the at least partially ordered liquidcrystal material has at least a first general direction, and at leastpartially setting at least a portion of the at least partially orderedliquid crystal material. Although not limiting herein, according to thisnon-limiting embodiment, the at least partial coating can have thicknessof at least 10 microns, and further can have a thickness ranging from 50to 1000 microns.

As previous mentioned, ordering a liquid crystal material by aligningthe liquid crystal material with another structure having an orientedsurface can take a substantial amount of time and/or can result inalignment of only certain portions of the liquid crystal materialadjacent the oriented surface. However, the inventors have observed thatby using certain non-contact methods of ordering, or combinations ofcontact and non-contact methods of ordering, faster and/or more completeordering liquid crystal materials can result. Thus, according to theabove-mentioned non-limiting embodiment, although not required, at leastpartially ordering at least a portion of the liquid crystal material cancomprise at least one of exposing at least a portion of the liquidcrystal material to a magnetic field or an electric field. Additionally,according to this non-limiting embodiment, ordering at least a portionof the liquid crystal material can comprise exposing at least a portionof the liquid crystal material to a magnetic field or an electric fieldwhile aligning the at least a portion of the liquid crystal materialwith another structure, such as, but not limited to a coating of anleast partially ordered liquid crystal material or an orientationfacility. Non-limiting examples of orientation facilities are describedbelow in more detail.

For example, according to one specific non-limiting embodiment formingthe at least partial coating can comprise applying a solution or mixtureof a liquid crystal polymer in a solvent or carrier to at least aportion of the optical substrate such that the liquid crystal polymerhas a thickness of greater than 6 microns. Thereafter, according to thisnon-limiting embodiment, at least a portion of the liquid crystalpolymer can be at least partially ordered by exposing the at least aportion of the liquid crystal polymer to at least one of a magneticfield and an electric field. Further, at least a portion of the liquidcrystal polymer can be at least partially ordered by exposing theportion to at least one of a magnetic field and an electric field whilealigning the at least a portion with another structure. After at leastpartially ordering at least a portion of the liquid crystal polymer, atleast a portion of the liquid crystal polymer can be at least partiallysetting, for example by drying at least a portion of the liquid crystalpolymer as discussed above.

Referring now to FIG. 1, one non-limiting embodiment provides a methodof making an alignment facility comprising an at least partial coatingcomprising an at least partially ordered liquid crystal material havingat least a first general direction on at least a portion of an opticalsubstrate by placing at least portion of a surface 10 of an opticalsubstrate 12 adjacent a surface 14 of a transparent mold 16 to define amolding region 17. The surface 14 of transparent mold 16 can be concaveor spherically negative, or it can have any other configuration asdesired or required. Further, although not required, a gasket or spacer15 can be placed between optical substrate 12 and transparent mold 16 toprovide a desired offset and/or contain the liquid crystal material.After positioning the optical substrate 12, a liquid crystal material 18can be introduced into the molding region 17 defined by the surface 10of the optical substrate 12 and the surface 14 of the transparent mold16, such that at least a portion of the liquid crystal material 18 iscaused to flow therebetween. Thereafter, at least a portion of theliquid crystal material 18 can be at least partially ordered, forexample, by exposure to an electric field, a magnetic field, linearlypolarized infrared radiation, linearly polarized ultraviolet radiation,and/or linearly polarized visible radiation and at least partiallypolymerized. After polymerization, the optical substrate with the atleast partial coating of an at least partially ordered liquid crystalmaterial connected to at least a portion of a surface thereof can bereleased from the mold.

Alternatively, the liquid crystal material 18 can be introduced ontosurface 14 of transparent mold 16 prior to placing at least a portion ofsurface 10 of the optical substrate 12 adjacent thereto such that atleast a portion of surface 10 contacts at least a portion of the liquidcrystal material 18, thereby causing the liquid crystal material 18 toflow between surface 10 and surface 14. Thereafter, the liquid crystalmaterial 18 can be at least partially ordered and polymerized asdiscussed above. After polymerization, the optical substrate 12 with theat least partial coating of liquid crystal material 18 connected theretocan be released from the mold.

Although not shown in FIG. 1, additionally or alternatively, anorientation facility having at least a first general direction can beimparted onto at least a portion of the surface of the transparent moldprior to introducing the liquid crystal material into the mold and/oronto at least a portion of the surface of the optical substrate prior tocontacting the surface of the optical substrate with the liquid crystalmaterial. Further, according to this non-limiting embodiment, at leastpartially ordering at least a portion of the liquid crystal material cancomprise at least partially aligning at least a portion of the liquidcrystal material with at least a portion of the orientation facility onthe surface of the mold and/or at least a portion of the orientationfacility on the surface of the optical substrate. Additionally, asdiscussed above, at least a portion of the liquid crystal material ofthe at least partial coating can be exposed to a magnetic field, anelectric field, linearly polarized infrared radiation, linearlypolarized ultraviolet radiation and/or linearly polarized visibleradiation during alignment to facilitate the processes.

Although not limiting herein, it is contemplated that the aforementionedovermolding methods of making at least partial coatings can beparticularly useful in forming coatings on multi-focal ophthalmiclenses, or for forming at least partial coatings for other applicationswhere relatively thick alignment facilities are desired.

Non-limiting examples of liquid crystal materials suitable for use inthe alignment facilities according to various non-limiting embodimentsdisclosed herein include liquid crystal polymers, liquid crystalpre-polymers, liquid crystal monomers, and liquid crystal mesogens. Forexample, according to one non-limiting embodiment, the liquid crystalmaterials of the first at least partial coating and the at least oneadditional at least partial coating can be independently chosen fromliquid crystal polymers, liquid crystal pre-polymers, liquid crystalmonomers, and liquid crystal mesogens. As used herein the term“pre-polymer” means partially polymerized materials.

Liquid crystal monomers that are suitable for use in conjunction withvarious non-limiting embodiments disclosed herein include mono- as wellas multi-functional liquid crystal monomers. Further, according tovarious non-limiting embodiments disclosed herein, the liquid crystalmonomer can be a cross-linkable liquid crystal monomer, and can furtherbe a photocross-linkable liquid crystal monomer. As used herein the term“photocross-linkable” means a material, such as a monomer, a pre-polymeror a polymer, that can be cross-linked on exposure to actinic radiation.For example, photocross-linkable liquid crystal monomers include thoseliquid crystal monomers that are cross-linkable on exposure toultraviolet radiation and/or visible radiation, either with or withoutthe use of polymerization initiators.

Non-limiting examples of cross-linkable liquid crystal monomers suitablefor use in accordance with various non-limiting embodiments disclosedherein include liquid crystal monomers having functional groups chosenfrom acrylates, methacrylates, allyl, allyl ethers, alkynes, amino,anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates,siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers and blendsthereof. Non-limiting examples of photocross-linkable liquid crystalmonomers suitable for use in the at least partial coatings of thealignment facilities according to various non-limiting embodimentsdisclosed herein include liquid crystal monomers having functionalgroups chosen from acrylates, methacrylates, alkynes, epoxides, thiols,and blends thereof.

Liquid crystal polymers and pre-polymers that are suitable for use inconjunction with various non-limiting embodiments disclosed hereininclude main-chain liquid crystal polymers and pre-polymers andside-chain liquid crystal polymers and pre-polymers. In main-chainliquid crystal polymers and pre-polymers, rod- or disc-like groupsand/or liquid crystal mesogens are primarily located within polymerbackbone. In side-chain polymers and pre-polymers, the rod- or disc-likegroups and/or liquid crystal mesogens primarily are located within theside chains of the polymer. Additionally, according to variousnon-limiting embodiments disclosed herein, the liquid crystal polymer orpre-polymer can be cross-linkable, and further can bephotocross-linkable.

Non-limiting examples of liquid crystal polymers and pre-polymers thatare suitable for use in accordance with various non-limiting embodimentsdisclosed herein include, but are not limited to, main-chain andside-chain polymers and pre-polymers having functional groups chosenfrom acrylates, methacrylates, allyl, allyl ethers, alkynes, amino,anhydrides, epoxides, hydroxides, isocyanates, blocked isocyanates,siloxanes, thiocyanates, thiols, urea, vinyl, vinyl ethers, and blendsthereof. Non-limiting examples of photocross-linkable liquid crystalpolymers and pre-polymers that are suitable for use in the at leastpartial coatings of the alignment facilities according to variousnon-limiting embodiments disclosed herein include those polymers andpre-polymers having functional groups chosen from acrylates,methacrylates, alkynes, epoxides, thiols, and blends thereof.

Liquid crystals mesogens that are suitable for use in conjunction withvarious non-limiting embodiments disclosed herein include thermotropicliquid crystal mesogens and lyotropic liquid crystal mesogens. Further,non-limiting examples of liquid crystal mesogens that are suitable foruse in conjunction with various non-limiting embodiments disclosedherein include columatic (or rod-like) liquid crystal mesogens anddiscotic (or disc-like) liquid crystal mesogens.

Further, although not limiting herein, the methods of making alignmentfacilities according to various non-limiting embodiments disclosedherein can further comprise forming an at least partial primer coatingon at least a portion of the optical substrate prior to applying any ofthe various at least partial coatings comprising a liquid crystalmaterial thereto to facilitate one or more of adhesion and wetting of atleast a portion of the optical substrate by the liquid crystal material.Non-limiting examples of primer coatings that can be used in conjunctionwith various non-limiting embodiments disclosed herein include coatingscomprising coupling agents, at least partial hydrolysates of couplingagents, and mixtures thereof. As used herein “coupling agent” means amaterial having at least one group capable of reacting, binding and/orassociating with a group on at least one surface. In one non-limitingembodiment, a coupling agent can serve as a molecular bridge at theinterface of at least two surfaces that can be similar or dissimilarsurfaces. Although not limiting herein, coupling agents, can bemonomers, oligomers, pre-polymers and/or polymers. Such materialsinclude, but are not limited to, organo-metallics such as silanes,titanates, zirconates, aluminates, zirconium aluminates, hydrolysatesthereof and mixtures thereof. As used herein the phrase “at leastpartial hydrolysates of coupling agents” means that at least some to allof the hydrolyzable groups on the coupling agent are hydrolyzed. Inaddition to coupling agents and/or hydrolysates of coupling agents, theprimer coatings can comprise other adhesion enhancing ingredients. Forexample, although not limiting herein, the primer coating can furthercomprise an adhesion-enhancing amount of an epoxy-containing material.Adhesion-enhancing amounts of an epoxy-containing material when added tothe coupling agent containing coating composition can improve theadhesion of a subsequently applied coating as compared to a couplingagent containing coating composition that is essentially free of theepoxy-containing material. Other non-limiting examples of primercoatings that are suitable for use in conjunction with the variousnon-limiting embodiments disclosed herein include those described U.S.Pat. Nos. 6,602,603 and 6,150,430, which are hereby specificallyincorporated by reference. Further, according to one non-limitingembodiment, the primer coating can serve as a barrier coating to preventinteraction of the coating ingredients with the substrate surface andvice versa.

Another non-limiting embodiment of a method of making an alignmentfacility for an optical dye on at least a portion of an ophthalmicsubstrate comprises imparting an orientation facility having at leastone general direction to at least portion of the ophthalmic substrate,forming a first at least partial coating comprising an at leastpartially ordered liquid crystal material having at least a firstgeneral direction that is generally parallel to at least one generaldirection of the orientation facility on at least a portion of theorientation facility, and thereafter forming at least one additional atleast partial coating comprising an at least partially ordered liquidcrystal material having at least a second general direction that isgenerally parallel to at least the first general direction of the firstat least partial coating on at least a portion of the first at leastpartial coating. Suitable non-limiting methods of forming at leastpartial coating comprising a liquid crystal material, as well assuitable non-limiting examples of liquid crystal materials that can beused to form such coatings, are set forth above.

As used herein the term “orientation facility” means a mechanism thatcan facilitate the positioning of one or more other structures that areexposed, directly and/or indirectly, to at least a portion of theorientation facility. Although not required, as discussed above withrespect to the various at least partial coatings comprising liquidcrystal materials, the orientation facilities according to variousnon-limiting embodiments disclosed herein can comprise a first orderedregion having a first general direction and at least one second orderedregion adjacent the first ordered region having an second generaldirection that is different from the first general direction. Further,the orientation facilities can have a plurality of regions, each ofwhich has a general direction that is the same or different from theremaining regions, so as to form a desired pattern or design.Additionally, the orientation facilities can comprise one or moredifferent types of orientation facilities.

Non-limiting examples of orientation facilities that can be used inconjunction with various other non-limiting embodiments disclosed hereininclude at least partial coatings comprising an at least partiallyordered alignment medium, at least partially ordered polymer sheets, atleast partially treated surfaces, Langmuir-Blodgett films, andcombinations thereof.

For example, although not limiting herein, according to variousnon-limiting embodiments wherein the orientation facility comprises anat least partial coating comprising an at least partially orderedalignment medium, imparting the orientation facility can compriseapplying an alignment medium to at least a portion of the opticalsubstrate and at least partially ordering the alignment medium.Non-limiting methods of ordering at least a portion of the alignmentmedium include those methods of ordering the at least partial coatingcomprising a liquid crystal material described above. For example,although not limiting herein, in one non-limiting embodiment, thealignment medium can be at least partially ordered by exposure to atleast one of: a magnetic field, an electric field, linearly polarizedinfrared radiation, linearly polarized ultraviolet radiation, linearlypolarized visible radiation and a shear force. Additionally, when thealignment medium is a photo-orientation material (discussed below), thealignment medium can be ordered using linearly polarized ultravioletradiation. Non-limiting examples of suitable alignment media that can beused in conjunction with various non-limiting embodiments disclosedherein include photo-orientation materials, and rubbed-orientationmaterials.

Non-limiting examples of photo-orientation materials that are suitablefor use as an alignment medium in conjunction with various non-limitingembodiments disclosed include photo-orientable polymer networks.Specific, non-limiting examples of suitable photo-orientable polymernetworks include azobenzene derivatives, cinnamic acid derivatives,coumarine derivatives, ferulic acid derivatives, and polyimides. Forexample, according to one non-limiting embodiment, the orientationfacility can comprise at least one at least partial coating comprisingan at least partially ordered photo-orientable polymer network chosenfrom azobenzene derivatives, cinnamic acid derivatives, coumarinederivatives, ferulic acid derivatives, and polyimides. Specificnon-limiting examples of cinnamic acid derivatives that can be used asan alignment medium in conjunction with various non-limiting embodimentsdisclosed herein include polyvinyl cinnamate and polyvinyl esters ofparamethoxycinnamic acid.

As used herein the term “rubbed-orientation material” means a materialthat can be at least partially ordered by rubbing at least a portion ofa surface of the material with another suitably textured material. Forexample, although not limiting herein, in one non-limiting embodiment,the rubbed-orientation material can be rubbed with a suitably texturedcloth or a velvet brush. Non-limiting examples of rubbed-orientationmaterials that are suitable for use as an alignment medium inconjunction with various non-limiting embodiments disclosed hereininclude (poly)imides, (poly)siloxanes, (poly)acrylates, and(poly)coumarines. Thus, for example, although not limiting herein, inone non-limiting embodiment, the at least partial coating comprising thealignment medium can be an at least partial coating comprising apolyimide that has been rubbed with velvet or a cloth so as to at leastpartially order at least a portion of the surface of the polyimide.

Further, as discussed above, the orientation facilities according tocertain non-limiting embodiments disclosed herein can comprise an atleast partially ordered polymer sheet. For example, although notlimiting herein, a sheet of polyvinyl alcohol (“PVA”) can be at leastpartially ordered by stretching the polymer sheet to at least, andthereafter the sheet can be connected to at least a portion of a surfaceof the optical substrate to form the orientation facility.Alternatively, the ordered polymer sheet can be made by a method that atleast partially orders the polymer chains during fabrication, forexample and without limitation, by extrusion. Still further, the atleast partially ordered polymer sheet can be made usingphoto-orientation methods. For example and without limitation, an sheetof a photo-orientation material can be formed, for example by cast, andat least partially ordered by exposure to linearly polarized UVradiation.

Still further, the orientation facilities according to variousnon-limiting embodiments disclosed herein can comprise an at leastpartially treated surface. As used herein, the term “treated surface”refers to at least a portion of a surface that has been physicallyaltered to create at least one ordered region on least a portion of thesurface. Non-limiting examples of at least partially treated surfacesinclude at least partially rubbed surfaces, at least partially etchedsurfaces, and at least partially embossed surfaces. Further, the atleast partially treated surfaces can be patterned, for example using aphotolithographic or interferographic process. Non-limiting examples ofat least partially treated surfaces that are useful in forming theorientation facilities according to various non-limiting embodimentsdisclosed herein include, chemically etched surfaces, plasma etchedsurfaces, nanoetched surfaces (such as surfaces etched using a scanningtunneling microscope or an atomic force microscope), laser etchedsurfaces, and electron-beam etched surfaces.

In one specific non-limiting embodiment, wherein the orientationfacility comprises an at least partially treated surface, imparting theorientation facility can comprise depositing a metal salt (such as ametal oxide or metal fluoride) onto at least a portion of a surface, andthereafter etching the deposit to form the orientation facility.Non-limiting examples of suitable techniques for depositing a metal saltinclude plasma vapor deposition, chemical vapor deposition, andsputtering. Non-limiting examples of etching processes are set forthabove.

As used herein the term “Langmuir-Blodgett films” means one or more atleast partially ordered molecular films on a surface. For example,although not limiting herein, a Langmuir-Blodgett film can be formed bydipping a substrate into a liquid one or more times so that it is atleast partially covered by a molecular film and then removing thesubstrate from the liquid such that, due to the relative surfacetensions of the liquid and the substrate, the molecules of the molecularfilm are at least partially ordered in a general direction. As usedherein, the term molecular film refers to monomolecular films (i.e.,monolayers) as well as films comprising more than one monolayer.

Another non-limiting embodiment provides a method of making an alignmentfacility for an optical dye on at least a portion of an opticalsubstrate comprising forming an at least partial coating comprising anat least partially ordered phase-separated polymer on at least a portionof the optical substrate. According to this non-limiting embodiment,forming the at least partial coating can comprise applying aphase-separating polymer system comprising a matrix phase formingmaterial and a guest phase forming material onto at least a portion ofthe optical substrate, and thereafter, at least partially ordering atleast a portion of the matrix phase forming material and at least aportion of the guest phase forming material such that at least a portionof the matrix phase forming material has at least a first generaldirection and at least a portion of the guest phase forming material hasat least a second general direction that is generally parallel to atleast the first general direction. After at least partially ordering, atleast a portion of the guest phase forming material can be separatedfrom at least a portion of the matrix phase forming material by at leastone of polymerization induced phase-separation and solvent inducedphase-separation to form a matrix phase and a guest phase.

According to various non-limiting embodiments disclosed herein, thematrix phase forming material can comprise a liquid crystal materialchosen from liquid crystal monomers, liquid crystal pre-polymers, andliquid crystal polymers. Further, according to various non-limitingembodiments, the guest phase forming material can comprise a liquidcrystal material chosen from liquid crystal mesogens, liquid crystalmonomers, and liquid crystal polymers and pre-polymers. Non-limitingexamples of such materials are set forth in detail herein.

Non-limiting methods of at least partially ordering at least a portionof the of the matrix phase forming material and at least a portion ofthe guest phase forming material of the phase-separating polymer systeminclude those set forth above for ordering liquid crystal materials. Forexample, although not limiting herein, at least partially ordering atleast a portion of the matrix phase forming material and at least aportion of the guest phase forming material can comprise exposing theportions to at least one of: a magnetic field, an electric field,linearly polarized infrared radiation, linearly polarized ultravioletradiation, linearly polarized visible radiation and a shear force.Further, at least partially ordering the portions can comprise at leastpartially aligning the portions with an orientation facility, asdescribed in more detail below.

As previously discussed, after at least partially ordering at least aportion of the matrix phase forming material and the guest phase formingmaterial, at least a portion of the guest phase forming material can beseparated from at least a portion of the matrix phase forming materialby at least one of polymerization induced phase separation and solventinduced phase separation. For clarity the separation of the matrix andguest phase forming materials is described herein in relation to theguest phase forming material being separated from the matrix phaseforming material, however, it should be appreciated that this languageis intended to cover any separation between the two phase formingmaterials. That is, this language is intended to cover separation of theguest phase forming material from the matrix phase forming material andseparation of the matrix phase forming material from the guest phaseforming material, as well as, simultaneous separation of both phaseforming materials, or any combination thereof. Although not limitingherein, it is generally believed that during phase separation, thecomponents of the phase-separating system (i.e., the matrix and guestphase forming materials) will separate from each other by first forminga gel of nanoscale (that is, nanometer sized) zones of each phaseforming material. These zones will subsequently coalesce into distinctphase regions.

In one specific non-limiting embodiment, the phase-separating polymersystem can comprise a mixture of a matrix phase forming materialcomprising a liquid crystal monomer and a guest phase forming materialcomprising at least one liquid crystal mesogen. According to thisnon-limiting embodiment, causing a least a portion of the guest phaseforming material to separate from at least a portion of the matrix phaseforming material can comprise polymerization induced phase-separation.That is, at least a portion of the liquid crystal monomer of the matrixphase can be polymerized and thereby separated from at least a portionof the at least one liquid crystal mesogen of the guest phase formingmaterial. Non-limiting methods of polymerization that can be used inconjunction with various non-limiting embodiments disclosed hereininclude photo-induced polymerization and thermally-inducedpolymerization.

In another specific non-limiting embodiment, the phase-separatingpolymer system can comprise a mixture of a matrix phase forming materialcomprising a liquid crystal monomer and a guest phase forming materialcomprising a low viscosity liquid crystal monomer having a differentfunctionality from the liquid crystal monomer of the matrix phase. Asused herein, the term “low viscosity liquid crystal monomer,” refers toa liquid crystal monomer mixture or solution that is freely flowing atroom temperature. According to this non-limiting embodiment, causing atleast a portion of the guest phase forming material to separate from atleast a portion of the matrix phase forming material can comprisepolymerization induced phase-separation. That is, at least a portion ofthe liquid crystal monomer of the matrix phase can be polymerized underconditions that do not cause the liquid crystal monomer of the guestphase to polymerize. During polymerization of the matrix phase formingmaterial, the guest phase forming material will separate from the matrixphase forming material. Thereafter, in certain non-limiting embodiments,the liquid crystal monomer of the guest phase forming material can bepolymerized in a separate polymerization process.

In another specific non-limiting embodiment, the phase-separatingpolymer system can comprise a solution, in at least one common solvent,of a matrix phase forming material comprising a liquid crystal polymerand a guest phase forming material comprising a liquid crystal polymerthat is different from the liquid crystal polymer of the matrix phaseforming material. According to this non-limiting embodiment, causing atleast a portion of the guest phase forming material to separate from thematrix phase forming material can comprise solvent inducedphase-separation. That is, at least a portion of the at least one commonsolvent can be evaporated from the mixture of liquid crystal polymers,thereby causing the two phases to separate from each other.

Another non-limiting embodiment provides a method of making an alignmentfacility for an optical dye on at least a portion of an opticalsubstrate comprising imparting an orientation facility to at least aportion of the optical substrate and forming an at least partial coatingcomprising an at least partially ordered phase-separated polymer on atleast a portion of the orientation facility. According to thisnon-limiting embodiment, a phase-separating polymer system comprising amatrix phase forming material comprising a liquid crystal material and aguest phase forming material comprising a liquid crystal material can beapplied on at least a portion of the orientation facility. Thereafter,at least a portion of the matrix phase forming material and at least aportion of the guest phase forming material of the phase-separatingpolymer system can be at least partially ordered such that the at leastpartially ordered portion of the matrix phase forming material has atleast a first general direction and the at least partially orderedportion of the guest phase forming material has at least a secondgeneral direction that is generally parallel to at least the firstgeneral direction. After at least partially ordering at least a portionof the matrix phase forming material and the guest phase formingmaterial, at least a portion of the guest phase forming material isseparated from at least a portion of the matrix phase forming materialby at least one of polymerization induced phase-separation and solventinduced phase-separation.

Further, according to this non-limiting embodiment, at least partiallyordering at least a portion of the matrix phase forming material and atleast a portion of the guest phase forming material can comprisealigning the portions with at least a portion of the orientationfacility. Further, although not required, at least a portion of thematrix phase forming material and the at least a portion of the guestphase forming material can be exposed to at least one of: a magneticfield, an electric field, linearly polarized infrared radiation,linearly polarized ultraviolet radiation, linearly polarized visibleradiation and a shear force to at least partially order the portion,either alone or in combination with aligning the portion with theorientation facility. Non-limiting methods of imparting the orientationfacility, as well as suitable non-limiting methods and materials forforming the at least partial coating comprising the phase-separatedpolymer are set forth above in detail.

Generally speaking, the thickness of the at least partial coatingcomprising the at least partially ordered phase-separated polymer of thealignment facilities according to various non-limiting embodimentsdisclosed herein can be chosen so as to achieve the desired overallthickness of the alignment facility. For example and without limitation,according to various non-limiting embodiments, the thickness of the atleast partial coating comprising the phase-separated polymer can rangefrom: 1 micron to 100 microns, from 10 microns to 50 microns, and from20 microns to 40 microns.

As previously discussed, generally, the time required to align a liquidcrystal material will depend, in part, upon the thickness of the liquidcrystal material. However, by forming an at least partial coatingcomprising a phase-separated polymer according to various non-limitingembodiments disclosed herein, the time required to align the liquidcrystal materials of the phase-separating polymer system can be reducedas compared to the time required to align a single-phase coating of aliquid crystal material having the same thickness. For example, in onenon-limiting embodiment, an at least partial coating comprising aphase-separated polymer and having a thickness ranging from 15 to 20microns can be formed on at least a portion of a orientation facilitycomprising an at least partially ordered photo-orientation material.Further, according to this non-limiting embodiment, at least partiallyaligning at least a portion of the matrix phase and at least a portionof the guest phase of the phase-separating polymer system can comprisewaiting less than 30 minutes.

Another non-limiting embodiment provides a method of making an alignmentfacility for an optical dye, the method comprising forming a sheetcomprising (i) an at least partially ordered liquid crystal polymerhaving at least a first general direction, and (ii) an at leastpartially ordered liquid crystal material distributed within at least aportion of the at least partially ordered liquid crystal polymer.Further, according to this non-limiting embodiment, the at leastpartially ordered liquid crystal material distributed within the atleast a portion of the at least partially ordered liquid crystal polymercan have at least a second general direction that is generally parallelto at least the first general direction of the liquid crystal polymer.

For example, although not limiting herein, according to one non-limitingembodiment, forming the sheet comprising the at least partially orderedliquid crystal polymer and the at least partially ordered liquid crystalmaterial distributed within at least a portion the at least partiallyordered liquid crystal polymer can comprise applying a phase-separatingpolymer system comprising a matrix phase forming material comprising aliquid crystal material and a guest phase forming material comprising aliquid crystal material on to at least a portion a substrate.Thereafter, at least a portion of the matrix phase forming material andat least a portion of the guest phase forming material can be at leastpartially ordered. After at least partially ordering at least a portionof the phase forming materials, at least a portion of the guest phaseforming material can be separated from at least a portion of the matrixphase forming material by at least one of polymerization inducedphase-separation and solvent induced phase-separation, and the at leastpartially ordered, phase-separated polymer coating can be removed fromthe substrate to form the sheet.

According to another non-limiting embodiment, forming the sheetcomprising the at least partially ordered liquid crystal polymer matrixand the at least partially ordered liquid crystal material distributedwithin at least a portion the at least partially ordered liquid crystalpolymer matrix can comprise forming an at least partially ordered liquidcrystal polymer sheet, and imbibing at least one liquid crystal mesogeninto at least a portion of the at least partially ordered liquid crystalpolymer sheet. For example, according to this non-limiting embodiment, asheet comprising a liquid crystal polymer can be formed and at leastpartially ordered by a method of forming a polymer sheet that can atleast partially order the liquid crystal polymer during formation, forexample, by extrusion. Alternatively, a liquid crystal polymer can becast onto a substrate and at least partially ordered by one of thenon-limiting methods of at least partially ordering liquid crystalmaterials set forth above. For example, although not limiting herein, atleast a portion of the liquid crystal material can be exposed to amagnetic or an electric field. After being at least partially ordered,the liquid crystal polymer can be at least partially set and removedfrom the substrate to form a sheet comprising an at least partiallyordered liquid crystal polymer matrix. Still further, a liquid crystalpolymer sheet can be cast, at least partially set, and subsequentlystretched to form sheet comprising an at least partially ordered liquidcrystal polymer.

After forming the sheet comprising the at least partially ordered liquidcrystal polymer, at least one liquid crystal mesogen can be imbibed intoat least a portion of the liquid crystal polymer sheet. For example,although not limiting herein, liquid crystal mesogens can be imbibedinto at least a portion of the liquid crystal polymer by applying asolution or mixture of the liquid crystal mesogens in a carrier to aportion of the liquid crystal polymer and, thereafter, allowing theliquid crystal mesogens to diffuse into the liquid crystal polymersheet, either with or without heating. Alternatively, the liquid crystalpolymer sheet can be immersed into a solution or mixture of the liquidcrystal mesogens in a carrier and the liquid crystal mesogens can beimbibed into the liquid crystal polymer sheet by diffusion, either withor without heating.

According to still another non-limiting embodiment, forming the sheetcomprising the at least partially ordered liquid crystal polymer and theat least partially ordered liquid crystal material distributed within atleast a portion of the at least partially ordered liquid crystal polymercan comprise forming a liquid crystal polymer sheet, imbibing at least aportion of the liquid crystal polymer sheet with at least one liquidcrystal mesogen, and thereafter at least partially ordering at leastportion of the liquid crystal polymer and at least a portion of the atleast one liquid crystal mesogen distributed therein. Although notlimiting herein, for example, at least a portion of the liquid crystalpolymer sheet and at least a portion of the at least one liquid crystalmesogen distributed therein can be at least partially ordered bystretching the liquid crystal polymer sheet. Further according to thisnon-limiting embodiment, the liquid crystal polymer sheet can be formedusing conventional polymer processing techniques, such as, but notlimited to, extrusion and casting.

Generally speaking, the sheets comprising the at least partially orderedliquid crystal polymer and the at least partially ordered liquid crystalmaterial distributed therein according to various non-limitingembodiments disclosed herein can have any thickness necessary so as toachieve the desired overall thickness of the alignment facility. Forexample, in one non-limiting embodiment, the thickness of the sheet canrange from 1 micron to 100 microns. In another non-limiting embodiment,the thickness of the sheet can range from 10 microns to 50 microns. Instill another non-limiting embodiment, the thickness of the sheet canrange from 20 microns to 40 microns.

According to specific non-limiting embodiments, the present disclosureprovides for a phase-separating polymer system comprising at least onephotoactive material. According to certain non-limiting embodiments, thepresent disclosure provides a phase-separating polymer system comprisingan at least partially cured matrix phase comprising a polymeric residueof at least a first liquid crystal monomer, and a guest phase comprisingat least one photoactive material and at least one liquid crystalmaterial, wherein at least a portion of the guest phase separates fromat least a portion of the matrix phase during the at least partialcuring of the polymeric residue of the at least first liquid crystalmonomer, for example by polymerization induced phase-separation.Non-limiting embodiments of the phase-separating polymer systemsdisclosed herein, include systems which may phase separate by eitherpolymerization induced phase-separation and solvent inducedphase-separation. According to these embodiments, the at least onephotoactive material may be selected from photochromic compounds,dichroic compounds, and photochromic-dichroic compounds. As used hereinthe term “residue” when used in reference to a monomer in apolymerization means that which remains of the monomer once it isincorporated into the polymeric structure. As used herein the terms“curing”, “cure”, “cured” or “at least partially cured” include an atleast partial polymerization and/or at least partial cross linkingprocess.

According to certain non-limiting embodiments, at least one photoactivematerial may comprise at least one photochromic compound. The at leastone photochromic compound may comprise a compound with a photochromicgroup chosen from a thermally or non-thermally reversible pyran, athermally or non-thermally reversible oxazine, or a thermally ornon-thermally reversible fulgide. Alternatively or in addition, the atleast one photochromic compound may comprise inorganic photochromiccompounds.

Non-limiting examples of thermally reversible photochromic pyrans fromwhich the at least one photochromic compound may be chosen and that maybe used in conjunction with various non-limiting embodiments disclosedherein include benzopyrans, naphthopyrans, e.g., naphtho[1,2-b]pyrans,naphtho[2,1-b]pyrans, indeno-fused naphthopyrans, such as thosedisclosed in U.S. Pat. No. 5,645,767 at col. 2, line 16 to col. 12, line57; heterocyclic-fused naphthopyrans, such as those disclosed in U.S.Pat. No. 5,723,072 at col. 2, line 27 to col. 15, line 55; U.S. Pat. No.5,698,141 at col. 2, line 11 to col. 19, line 45; U.S. Pat. No.6,153,126 at col. 2, line 26 to col. 8, line 60; and U.S. Pat. No.6,022,497 at col. 2, line 21 to col. 11, line 46, which are all herebyincorporated by reference; spiro-9-fluoreno[1,2-b]pyrans;phenanthropyrans; quinopyrans; fluoroanthenopyrans; spiropyrans, e.g.,spiro(benzindoline)naphthopyrans, spiro(indoline)benzopyrans,spiro(indoline)naphthopyrans, spiro(indoline)quinopyrans andspiro(indoline)pyrans. More specific examples of naphthopyrans and thecomplementary organic photochromic substances are described in U.S. Pat.No. 5,658,501 at col. 1, line 64 to col. 13, line 17, which is herebyspecifically incorporated by reference herein. Spiro(indoline)pyrans arealso described in the text, Techniques in Chemistry, Volume III,“Photochromism”, Chapter 3, Glenn H. Brown, Editor, John Wiley and Sons,Inc., New York, 1971, which is hereby incorporated by reference.

Non-limiting examples of thermally reversible photochromic oxazines fromwhich the photochromic compounds may be chosen and that may be used inconjunction with various non-limiting embodiments disclosed hereininclude benzoxazines, naphthoxazines, and spiro-oxazines, e.g.,spiro(indoline)naphthoxazines, spiro(indoline)pyridobenzoxazines,spiro(benzindoline) pyridobenzoxazines,spiro(benzindoline)naphthoxazines, spiro(indoline)benzoxazines,spiro(indoline)fluoranthenoxazine, and spiro(indoline)quinoxazine.

Non-limiting examples of thermally reversible photochromic fulgides fromwhich the photochromic compounds may be chosen and that may be used inconjunction with various non-limiting embodiments disclosed hereininclude: fulgimides, and the 3-furyl and 3-thienyl fulgides andfulgimides, which are disclosed in U.S. Pat. No. 4,931,220 at column 2,line 51 to column 10, line 7, which is hereby specifically incorporatedby reference, and mixtures of any of the aforementioned photochromicmaterials/compounds. Non-limiting examples of non-thermally reversiblephotochromic compounds from which the photochromic compounds may bechosen and that may be used in conjunction with various non-limitingembodiments disclosed herein include the photochromic compoundsdisclosed in U.S. Patent Application Publication 2005/0004361 atparagraphs [0314] to [0317] which disclosure is hereby specificallyincorporated herein by reference.

In certain non-limiting embodiments, the photochromic compound may be aninorganic photochromic compound. Non-limiting examples of suitableinclude crystallites of silver halide, cadmium halide and/or copperhalide. Other non-limiting examples of inorganic photochromic materialsmay be prepared by the addition of europium(II) and/or cerium(II) to amineral glass, such as a soda-silica glass. According to onenon-limiting embodiment, the inorganic photochromic compounds may beadded to molten glass and formed into particles that are incorporatedinto the compositions of the present disclosure to form microparticlescomprising such particulates. The glass particulates may be formed byany of a number of various methods known in the art. Suitable inorganicphotochromic materials are further described in Kirk Othmer Encyclopediaof Chemical Technology, 4th ed., volume 6, pages 322-325, the disclosureof which is incorporated by reference herein.

As set forth herein, in certain non-limiting embodiments the at leastone photochromic compound may be at least one photochromic pyran.According to these non-limiting embodiments, the at least onephotochromic compound may be represented by Formula II:

With reference to Formula II, A may be a substituted or unsubstitutedaromatic ring or a substituted or unsubstituted fused aromatic ringchosen from: naphtho, benzo, phenanthro, fluorantheno, antheno,quinolino, thieno, furo, indolo, indolino, indeno, benzofuro,benzothieno, thiopheno, indeno-fused naphtho, heterocyclic-fusednaphtho, or heterocyclic-fused benzo. According to these non-limitingembodiments, the possible substituents on the aromatic or fused aromaticring are disclosed in U.S. Pat. Nos. 5,458,814; 5,466,398; 5,514,817;5,573,712; 5,578,252; 5,637,262; 5,650,098; 5,651,923; 5,698,141;5,723,072; 5,891,368; 6,022,495; 6,022,497; 6,106,744; 6,149,841;6,248,264; 6,348,604; 6,736,998; 7,094,368; 7,262,295; and 7,320,826,the disclosures of which are incorporated by reference herein. Accordingto Formula II, “i” may be the number of substituent(s) R′ (which may bethe same or different) attached to ring A and may range from 0 to 10.Further, with reference to Formula II, B and B′ may each independentlyrepresent a group chosen from:

-   -   a metallocenyl group (such as those described in U.S. Patent        Application Publication 2007/0278460 at paragraph [0008] to        [0036] which disclosure is specifically incorporated by        reference herein);    -   an aryl group that is mono-substituted with a reactive        substituent or a compatiblizing substituent (such as those        discussed in U.S. Patent Application Publication 2007/0278460 at        paragraph [0037] to [0059] which disclosure is specifically        incorporated by reference herein);    -   9-julolidinyl, an unsubstituted, mono-, di- or tri-substituted        aryl group chosen from phenyl and naphthyl, an unsubstituted,        mono- or di-substituted heteroaromatic group chosen from        pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,        benzothien -2-yl, benzothien-3-yl, dibenzofuranyl,        dibenzothienyl, carbazoyl, benzopyridyl, indolinyl and        fluorenyl, wherein the aryl and heteroaromatic substituents are        each independently: hydroxy, aryl, mono- or        di-(C₁-C₁₂)alkoxyaryl, mono- or di-(C₁-C₁₂)alkylaryl, haloaryl,        C₃-C₇ cycloalkylaryl, C₃-C₇ cycloalkyl, C₃-C₇ cycloalkyloxy,        C₃-C₇ cycloalkyloxy(C₁-C₁₂)alkyl, C₃-C₇        cycloalkyloxy(C₁-C₁₂)alkoxy, aryl(C₁-C₁₂)alkyl,        aryl(C₁-C₁₂)alkoxy, aryloxy, aryloxy(C₁-C₁₂)alkyl,        aryloxy(C₁-C₁₂)alkoxy, mono- or        di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- or        di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, mono- or        di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, mono- or        di-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy, amino, mono- or        di-(C₁-C₁₂)alkylamino, diarylamino, piperazino,        N—(C₁-C₁₂)alkylpiperazino, N-arylpiperazino, aziridino,        indolino, piperidino, morpholino, thiomorpholino,        tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidino, C₁-C₁₂        alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy,        mono(C₁-C₁₂)alkoxy(C₁-C₁₂) alkyl, acryloxy, methacryloxy,        halogen or —C(═O)R¹, wherein R¹ represents a group, such as,        —OR², —N(R³)R⁴, piperidino or morpholino, wherein R² represents        a group, such as, allyl, C₁-C₆ alkyl, phenyl, mono(C₁-C₆)alkyl        substituted phenyl, mono(C₁-C₆)alkoxy substituted phenyl,        phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substituted        phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted        phenyl(C₁-C₃)alkyl, C₁-C₆ alkoxy(C₂-C₄)alkyl or C₁-C₆ haloalkyl,        and R³ and R⁴ each independently represents a group, such as,        C₁-C₆ alkyl, C₅-C₇ cycloalkyl or a substituted or an        unsubstituted phenyl, wherein said phenyl substituents are each        independently C₁-C₆ alkyl or C₁-C₆ alkoxy;    -   an unsubstituted or mono-substituted group chosen from        pyrazolyl, imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidino,        phenothiazinyl, phenoxazinyl, phenazinyl and acridinyl, wherein        said substituents are each independently C₁-C₁₂ alkyl, C₁-C₁₂        alkoxy, phenyl or halogen;    -   a 4-substituted phenyl, the substituent being a dicarboxylic        acid residue or derivative thereof, a diamine residue or        derivative thereof, an amino alcohol residue or derivative        thereof, a polyol residue or derivative thereof, —(CH₂)—,        —(CH₂)_(k)— or —[O—(CH₂)_(k)]_(q)—, wherein “k” represents an        integer ranging from 2 to 6 and “q” represents an integer        ranging from 1 to 50, and wherein the substituent is connected        to an aryl group of another photochromic material;    -   a group represented by:

-   -    wherein W represents a group, such as, —CH₂— or oxygen; Y        represents a group, such as, oxygen or substituted nitrogen,        provided that when Y represents substituted nitrogen, W        represents —CH₂—, the substituted nitrogen substituents being        hydrogen, C₁-C₁₂ alkyl or C₁-C₁₂ acyl; each R⁵ independently        represents a group, such as, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,        hydroxy or halogen; R⁶ and R⁷ each independently represent a        group, such as, hydrogen or C₁-C₁₂ alkyl; and “j” represents an        integer ranging from 0 to 2; or    -   a group represented by:

-   -    wherein R⁸ represents a group, such as, hydrogen or C₁-C₁₂        alkyl, and R⁹ represents a group, such as, an unsubstituted,        mono- or di-substituted naphthyl, phenyl, furanyl or thienyl,        wherein said naphthyl, phenyl, furanyl and thienyl substituents        are each independently C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or halogen.        Alternatively, B and B′ may represent groups that together form        a fluoren-9-ylidene or mono- or di-substituted        fluoren-9-ylidene, each of said fluoren-9-ylidene substituents        independently being C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy or halogen.

Further, with reference to Formula II, R′ may be a substituent on a ringin Formula II, wherein if R′ is a substituent on an sp³ hybridizedcarbon, each R′ may be independently selected from: a metallocenylgroup; a reactive substituent or a compatiblizing substituent;perhalo(C₁-C₁₀)alkyl, a perhalo(C₂-C₁₀)alkenyl, aperhalo(C₃-C₁₀)alkynyl, a perhalo(C₁-C₁₀)alkoxy or aperhalo(C₃-C₁₀)cycloalkyl; a group represented by—O(CH₂)_(a)(CJ₂)_(b)CK₃, wherein K is a halogen, J is hydrogen orhalogen, “a” is an integer ranging from 1 to 10, and “b” is an integerranging from 1 to 10; a silicon-containing group represented by one of

wherein R¹⁰, R¹¹, and R¹² are each independently C₁-C₁₀ alkyl, C₁-C₁₀alkoxy or phenyl; hydrogen, hydroxy, C₁-C₆ alkyl, chloro, fluoro, C₃-C₇cycloalkyl, allyl or C₁-C₈ haloalkyl; morpholino, piperidino,pyrrolidino, an unsubstituted, mono- or di-substituted amino, whereinsaid amino substituents are each independently C₁-C₆ alkyl, phenyl,benzyl or naphthyl; an unsubstituted, mono-, di- or tri-substituted arylgroup chosen from phenyl, naphthyl, benzyl, phenanthryl, pyrenyl,quinolyl, isoquinolyl, benzofuranyl, thienyl, benzothienyl,dibenzofuranyl, dibenzothienyl, carbazolyl or indolyl, wherein the arylgroup substituents are each independently halogen, C₁-C₆ alkyl or C₁-C₆alkoxy; —C(═O)R¹³, wherein R¹³ is hydrogen, hydroxy, C₁-C₆ alkyl, C₁-C₆alkoxy, amino, mono- or di-(C₁-C₆)alkylamino, morpholino, piperidino,pyrrolidino, an unsubstituted, mono- or di-substituted phenyl ornaphthyl, an unsubstituted, mono- or di-substituted phenoxy, anunsubstituted, mono- or di-substituted phenylamino, wherein said phenyl,naphthyl, phenoxy, and phenylamino substituents are each independentlyC₁-C₆ alkyl or C₁-C₆ alkoxy; —OR¹⁴, wherein R¹⁴ is C₁-C₆ alkyl,phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl, C₁-C₆alkoxy(C₂-C₄)alkyl, C₃-C₇ cycloalkyl, mono(C₁-C₄)alkyl substituted C₃-C₇cycloalkyl, C₁-C₈ chloroalkyl, C₁-C₈ fluoroalkyl, allyl or C₁-C₆ acyl,—CH(R¹⁵)R¹⁶, wherein R¹⁵ is hydrogen or C₁-C₃ alkyl, and R¹⁶ is —CN,—CF₃ or —COOR⁷, wherein R⁷ is hydrogen or C₁-C₃ alkyl, or —C(═O)R¹⁸,wherein R¹⁸ is hydrogen, C₁-C₆ alkyl, C₁-C₆ alkoxy, amino, mono- ordi-(C₁-C₆)alkylamino, an unsubstituted, mono- or di-substituted phenylor naphthyl, an unsubstituted, mono- or di-substituted phenoxy or anunsubstituted, mono- or di-substituted phenylamino, wherein said phenyl,naphthyl, phenoxy and phenylamino substituents are each independentlyC₁-C₆ alkyl or C₁-C₆ alkoxy; a 4-substituted phenyl, the substituentbeing a dicarboxylic acid residue or derivative thereof, a diamineresidue or derivative thereof, an amino alcohol residue or derivativethereof, a polyol residue or derivative thereof, —(CH₂)—, —(CH₂)_(k)— or—[O—(CH₂)_(k)]_(q)—, wherein “k” is an integer ranging from 2 to 6 and“q” is an integer ranging from 1 to 50, and wherein the substituent isconnected to an aryl group on another photochromic material; —CH(R¹⁹)₂,wherein R¹⁹ is —CN or —COOR²⁰, wherein R²⁰ is hydrogen, C₁-C₆ alkyl,C₃-C₇ cycloalkyl, phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkyl substitutedphenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₃)alkyl oran unsubstituted, mono- or di-substituted phenyl or naphthyl, whereinsaid phenyl and naphthyl substituents are each independently C₁-C₆ alkylor C₁-C₆ alkoxy; —CH(R²¹)R²², wherein R²¹ is hydrogen, C₁-C₆ alkyl or anunsubstituted, mono- or di-substituted phenyl or naphthyl, wherein saidphenyl and naphthyl substituents are each independently C₁-C₆ alkyl orC₁-C₆ alkoxy, and R²² is —C(═O)OR²³, —C(═O)R²⁴ or —CH₂OR²⁵, wherein R²³is hydrogen, C₁-C₆ alkyl, C₃-C₇ cycloalkyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxysubstituted phenyl(C₁-C₃)alkyl or an unsubstituted, mono- ordi-substituted phenyl or naphthyl, wherein said phenyl and naphthylsubstituents are each independently C₁-C₆ alkyl or C₁-C₆ alkoxy, R²⁴ ishydrogen, C₁-C₆ alkyl, amino, mono(C₁-C₆)alkylamino,di(C₁-C₆)alkylamino, phenylamino, diphenylamino, (mono- ordi-(C₁-C₆)alkyl substituted phenyl)amino, (mono- or di-(C₁-C₆)alkoxysubstituted phenyl)amino, di(mono- or di-(C₁-C₆)alkyl substitutedphenyl)amino, di(mono- or di-(C₁-C₆)alkoxy substituted phenyl)amino,morpholino, piperidino or an unsubstituted, mono- or di-substitutedphenyl or naphthyl, wherein said phenyl or naphthyl substituents areeach independently C₁-C₆ alkyl or C₁-C₆ alkoxy, and R²⁵ is hydrogen,—C(═O)R²³, C₁-C₆ alkyl, C₁-C₃ alkoxy (C₁-C₆)alkyl, phenyl(C₁-C₆)alkyl,mono-alkoxy substituted phenyl(C₁-C₆)alkyl or an unsubstituted, mono- ordi-substituted phenyl or naphthyl, wherein said phenyl or naphthylsubstituents are each independently C₁-C₆ alkyl or C₁-C₆ alkoxy; or twoR′ groups on the same atom together form an oxo group, aspiro-carbocyclic group containing 3 to 6 carbon atoms or aspiro-heterocyclic group containing 1 to 2 oxygen atoms and 3 to 6carbon atoms including the spirocarbon atom, said spiro-carbocyclic andspiro-heterocyclic groups being annellated with 0, 1 or 2 benzene rings;or

when R′ is a substituent on an sp² hybridized carbon, each R′ may beindependently: hydrogen; C₁-C₆ alkyl; chloro; fluoro; bromo; C₃-C₇cycloalkyl; an unsubstituted, mono- or di-substituted phenyl, whereinsaid phenyl substituents are each independently C₁-C₆ alkyl or C₁-C₆alkoxy; —OR²⁶ or —OC(═O)R²⁶ wherein R²⁶ is hydrogen, amine, alkyleneglycol, polyalkylene glycol, C₁-C₆ alkyl, phenyl(C₁-C₃)alkyl,mono(C₁-C₆)alkyl substituted phenyl(C₁-C₃)alkyl, mono(C₁-C₆)alkoxysubstituted phenyl(C₁-C₃)alkyl, (C₁-C₆)alkoxy(C₂-C₄)alkyl, C₃-C₇cycloalkyl, mono(C₁-C₄)alkyl substituted C₃-C₇ cycloalkyl or anunsubstituted, mono- or di-substituted phenyl, wherein said phenylsubstituents are each independently C₁-C₆ alkyl or C₁-C₆ alkoxy; areactive substituent or a compatiblizing substituent; a 4-substitutedphenyl, said phenyl substituent being a dicarboxylic acid residue orderivative thereof, a diamine residue or derivative thereof, an aminoalcohol residue or derivative thereof, a polyol residue or derivativethereof, —(CH₂)—, —(CH₂)_(k)— or —[O—(CH₂)_(k)]_(q)—, wherein “k” is aninteger ranging from 2 to 6, and “q” is an integer ranging from 1 to 50,and wherein the substituent is connected to an aryl group on anotherphotochromic material; —N(R²⁷)R²⁸, wherein R²⁷ and R²⁸ are eachindependently hydrogen, C₁-C₈ alkyl, phenyl, naphthyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, benzopyridyl,fluorenyl, C₁-C₈ alkylaryl, C₃-C₈ cycloalkyl, C₄-C₁₆ bicycloalkyl,C₅-C₂₀ tricycloalkyl or C₁-C₂₀ alkoxy(C₁-C₆)alkyl, or R²⁷ and R²⁸ cometogether with the nitrogen atom to form a C₃-C₂₀ hetero-bicycloalkylring or a C₄-C₂₀ hetero-tricycloalkyl ring; a nitrogen containing ringrepresented by:

wherein each —V—is independently chosen for each occurrence from —CH₂—,—CH(R²⁹)—, —C(R²⁹)₂—, —CH(aryl)-, —C(aryl)₂- and —C(R²⁹)(aryl)-, whereineach R²⁹ is independently C₁-C₆ alkyl and each aryl is independentlyphenyl or naphthyl; —U—is —V—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R²⁹)—or —N(aryl)-; “s” is an integer ranging from 1 to 3; and “r” is aninteger ranging from 0 to 3, provided that if “r” is 0 then —U—is thesame as —V—; a group represented by:

wherein each R³⁰ is independently C₁-C₆ alkyl, C₁-C₆ alkoxy, fluoro orchloro; R³¹, R³² and R³³ are each independently hydrogen, C₁-C₆ alkyl,phenyl or naphthyl, or R³¹ and R³² together form a ring of 5 to 8 carbonatoms; and “p” is an integer ranging from 0 to 3; or a substituted or anunsubstituted C₄-C₁₈ spirobicyclic amine or a substituted or anunsubstituted C₄-C₁₈ spirotricyclic amine, wherein said substituents areeach independently aryl, C₁-C₆ alkyl, C₁-C₆ alkoxy orphenyl(C₁-C₆)alkyl;

or R′ may be a metallocenyl group; perfluoroalkyl or perfluoroalkoxy;—C(═O)R³⁴ or —SO₂R³⁴, wherein each R³⁴ is independently hydrogen, C₁-C₆alkyl, —OR³⁵ or —NR³⁶R³⁷, wherein R³⁵, R³⁶ and R³⁷ are eachindependently hydrogen, C₁-C₆ alkyl, C₅-C₇ cycloalkyl, alkylene glycol,polyalkylene glycol or an unsubstituted, mono- or di-substituted phenyl,wherein said phenyl substituents are each independently C₁-C₆ alkyl orC₁-C₆ alkoxy; —C(═C(R³³)₂)R³⁹ wherein each R³³ is independently—C(═O)R³⁴, —OR³⁵, —OC(═O)R³⁵, —NR³⁶R³⁷, hydrogen, halogen, cyano, C₁-C₆alkyl, C₅-C₇ cycloalkyl, alkylene glycol, polyalkylene glycol or anunsubstituted, mono- or di-substituted phenyl, wherein said phenylsubstituents are each independently C₁-C₆ alkyl or C₁-C₆ alkoxy, and R³⁹is hydrogen, C₁-C₆ alkyl, C₅-C₇ cycloalkyl, alkylene glycol,polyalkylene glycol or an unsubstituted, mono- or di-substituted phenyl,wherein said phenyl substituents are each independently C₁-C₆ alkyl orC₁-C₆ alkoxy; or —C≡CR⁴⁰ or —C≡N wherein R⁴⁰ is —C(═O)R³⁴, hydrogen,C₁-C₆ alkyl, C₅-C₇ cycloalkyl or an unsubstituted, mono- ordi-substituted phenyl, wherein said phenyl substituents are eachindependently C₁-C₆ alkyl or C₁-C₆ alkoxy; or a least one pair ofadjacent R′ groups together form a group represented by:

wherein D and D′ are each independently oxygen or the group —NR²⁷—; ortwo R′ groups on adjacent atoms come together form an aromatic orheteroaromatic fused group, said fused group being benzo, indeno,dihydronaphthalene, indole, benzofuran, benzopyran or thianaphthene.

According to certain non-limiting embodiments, at least one photoactivematerial may comprise at least one dichroic compound. Suitable dichroiccompounds are described in detail in U.S. Pat. No. 7,097,303 at column7, lines 6 to 60, the disclosure of which is incorporated by referenceherein. Other non-limiting examples of suitable conventional dichroiccompounds include azomethines, indigoids, thioindigoids, merocyanines,indans, quinophthalonic dyes, perylenes, phthaloperines,triphenodioxazines, indoloquinoxalines, imidazo-triazines, tetrazines,azo and (poly)azo dyes, benzoquinones, naphthoquinones, anthroquinoneand (poly)anthroquinones, anthropyrimidinones, iodine and iodates. Inanother non-limiting embodiment, the at least one dichroic compound maybe at least one polymerizable dichroic compound. That is, according tothis non-limiting embodiment, the at least one dichroic material cancomprise at least one group that is capable of being polymerized (i.e.,a “polymerizable group” or “reactive group”). For example, although notlimiting herein, in one non-limiting embodiment the at least onedichroic compound can have at least one alkoxy, polyalkoxy, alkyl, orpolyalkyl substituent terminated with at least one polymerizable group.As described herein, dichroic compounds are capable of absorbing one oftwo orthogonal plane polarized components of transmitted radiation morestrongly than the other, thereby resulting in linear polarization of thetransmitted radiation. However, while dichroic compounds are capable ofpreferentially absorbing one of two orthogonal plane polarizedcomponents of transmitted radiation, if the molecules of the dichroiccompound are not aligned, no net linear polarization of transmittedradiation will be achieved. That is, due to the random positioning ofthe molecules of the dichroic compound, selective absorption by theindividual molecules can cancel each other such that no net or overalllinear polarizing effect is achieved. Thus, it is generally necessary toalign the molecules of a dichroic compound in order to achieve a netlinear polarization. An alignment facility such as described herein maybe used to facilitate the positioning of an optically anisotropiccompound, such as a dichroic compound or photochromic-dichroic compound,thereby achieving a desired optical property or effect.

According to certain non-limiting embodiments, at least one photoactivematerial may comprise at least one photochromic-dichroic compound. Asused herein the term “photochromic-dichroic” means displaying bothphotochromic and dichroic properties under certain conditions, whichproperties are at least detectable by instrumentation. Accordingly,“photochromic-dichroic compounds” are compounds displaying bothphotochromic and dichroic (i.e., linearly polarizing) properties undercertain conditions, which properties are at least detectable byinstrumentation. Thus, photochromic-dichroic compounds have anabsorption spectrum for at least visible radiation that varies inresponse to at least actinic radiation and are capable of absorbing oneof two orthogonal plane polarized components of at least transmittedradiation more strongly than the other. Additionally, as withconventional photochromic compounds discussed above, thephotochromic-dichroic compounds disclosed herein can be thermallyreversible. That is, the photochromic-dichroic compounds can switch froma first state to a second state in response to actinic radiation andrevert back to the first state in response to thermal energy.Non-limiting examples of suitable photochromic-dichroic compounds thatmay be included in the guest phases described herein include thosedisclosed in U.S. Patent Application Publication 2005/0012998 atparagraphs [0089] to [0339], which disclosure is incorporated byreference herein. In addition, a general structure for certainphotochromic-dichroic compounds suitable for use herein is presented inU.S. Pat. No. 7,342,112 at column 5, line 35 to column 31, line 3 andTable V spanning columns 97-102, which disclosure is incorporated byreference herein.

Further, according to various non-limiting embodiments disclosed herein,the guest phase may be adapted to allow the at least one photoactivematerial (i.e., the at least one photochromic compound, at least onedichroic compound, and/or at least one photochromic-dichroic compound)to switch from a first state to the second state at a desired rate andto revert back to the first state at a desired rate. Generally speaking,conventional photochromic/dichroic compounds can undergo atransformation from one isomeric form to another isomeric form inresponse to actinic radiation, with each isomeric form having acharacteristic absorption spectrum and/or polarization characteristic.The photochromic compound, dichroic compound, or photochromic-dichroiccompounds according to various non-limiting embodiments disclosed hereinmay undergo such an isomeric transformation. The rate or speed at whichthis isomeric transformation (and the reverse transformation) occursdepends, in part, upon the properties of material (i.e., the guestphase) surrounding the at least one photoactive material (i.e., the atleast one photochromic compound, at least one dichroic compound, and/orat least one photochromic-dichroic compound). Although not limitingherein, it is believed by the inventors the rate of transformation ofthe photochromic/dichroic compound(s) will depend, in part, upon theflexibility of the guest phase; that is, the mobility or viscosity ofthe components that make up the guest phase. In particular, while notlimiting herein, it is believed that the rate of transformation of thephotochromic compound(s), dichroic compound(s), and/orphotochromic-dichroic compound(s) will generally be faster in guestphases having a flexible composition than in guest phases having a stiffor rigid composition. Therefore, according to certain non-limitingembodiments disclosed herein, the guest phase may be adapted to allowthe at least one photochromic compound(s), dichroic compound(s), and/orphotochromic-dichroic compound(s) to transform between various isomericstates at desired rates. For example, although not limiting herein, theguest phase can be adapted by adjusting one or more of the structure,molecular weight, degree of polymerization, and the cross-link densityof the at least one liquid crystal material.

For example, according to various non-limiting embodiments disclosedherein, the at least one photochromic-dichroic compound can have a firststate having a first absorption spectrum, a second state having a secondabsorption spectrum that is different from the first absorptionspectrum, and can be adapted to switch from the first state to thesecond state in response to at least actinic radiation and to revertback to the first state in response to thermal energy. Further, thedichroic or photochromic-dichroic compound can be dichroic (i.e.,linearly polarizing) in one or both of the first state and the secondstate. For example, although not required, the dichroic orphotochromic-dichroic compounds can be linearly polarizing in anactivated colored state and non-polarizing in the bleached or faded(i.e., not activated) state. As used herein, the term “activated state”refers to the photochromic/dichroic compounds when exposed to sufficientactinic radiation to cause the at least a portion of thephotochromic/dichroic compounds to switch from a first state to a secondstate. Further, although not required, the dichroic orphotochromic-dichroic compounds can be dichroic in both the first andsecond states. While not limiting herein, for example, the dichroic orphotochromic-dichroic compounds can linearly polarize visible radiationin both the activated state and the bleached state. Further, in thisembodiment, the dichroic or photochromic-dichroic compounds can linearlypolarize visible radiation in an activated state and can linearlypolarize UV radiation in the bleached state.

In certain non-limiting embodiments of the phase-separating systemdescribed herein, the first liquid crystal monomer of the matrix phaseand/or the at least one liquid crystal material of the guest phase maybe a commercially available or known liquid crystal monomer or liquidcrystal material, respectively. Alternatively, in specific non-limitingembodiments of the phase-separating polymer system described herein, atleast one of the first liquid crystal monomer of the matrix phase andthe at least one liquid crystal material of the guest phase may compriseat least one mesogen containing compound having a structure representedby Formula I:

In Formula I, each X may be independently represented by: (i) a group—R; (ii) a group represented by the structure -(L)_(y)-R; (iii) a grouprepresented by the structure -(L)-R; (iv) a group represented by thestructure -(L)_(w)-Q; (v) a group represented by the structure:

(vi) a group represented by -(L)_(y)-P; or (vii) a group represented by-(L)_(w)-[(L)_(w)-P]_(y). Specific non-limiting examples of certainsuitable mesogen containing compounds represented by Formula I may befound in U.S. application Ser. No. 12/163,116, filed Jun. 27, 2008, atparagraphs [0021]-[0046], [0051]-[0055], and [0147]-[0213], includingTable 1, which disclosure is incorporated by reference herein. Further,in Formula I, each group P represents a reactive group. As used herein,the term “reactive group” means an atom, bond, or functional group thatmay react to form a bond, such as a covalent, polar covalent, or ionicbond with another molecule. For example, in certain non-limitingembodiments, a reactive group may react with a group, react with acomonomer or react with a reactive group on a developing polymer suchthat the structure corresponding to Formula I or a residue thereof isincorporated into the polymer. According to various non-limitingembodiment, each group P may be independently selected from reactivegroup such as a group Q, hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈alkyl, C₁-C₁₈ alkoxy, amino(C₁-C₁₈)alkylene, C₁-C₁₈ alkylamino,di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl ether,(C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkylene, polyethyleneoxy,polypropyleneoxy, ethylene, acryloyl, acryloyloxy(C₁-C₁₈)alkylene,methacryloyl, methacryloyloxy(C₁-C₁₈)alkylene, 2-chloroacryloyl,2-phenylacryloyl, acryloylphenylene, 2-chloroacryloylamino,2-phenylacryloylamino, oxetanyl, glycidyl, cyano,isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl ester,a styrene derivative, main-chain and side-chain liquid crystal polymers,siloxane derivatives, ethyleneimine derivatives, maleic acidderivatives, fumaric acid derivatives, unsubstituted cinnamic acidderivatives, cinnamic acid derivatives that are substituted with atleast one of methyl, methoxy, cyano and halogen, or substituted orunsubstituted chiral or non-chiral monovalent or divalent groups chosenfrom steroid radicals, terpenoid radicals, alkaloid radicals andmixtures thereof, wherein the substituents are independently chosen fromC₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl,C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano,cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures thereof.

Further, although not limiting herein, in certain non-limitingembodiments P may be a reactive group comprising a polymerizable group,wherein the polymerizable group may be any functional group adapted toparticipate in a polymerization reaction. Non-limiting examples ofpolymerization reactions include those described in the definition of“polymerization” in Hawley's Condensed Chemical Dictionary ThirteenthEdition, 1997, John Wiley & Sons, pages 901-902, which disclosure isincorporated herein by reference. For example, although not limitingherein, polymerization reactions include: “addition polymerization,” inwhich free radicals are the initiating agents that react with the doublebond of a monomer by adding to it on one side at the same time producinga new free electron on the other side; “condensation polymerization,” inwhich two reacting molecules combine to form a larger molecule withelimination of a small molecule, such as a water molecule; and“oxidative coupling polymerization.” In an additional non-limitingembodiment, P may be an unsubstituted or substituted ring openingmetathesis polymerization precursor. Further, non-limiting examples ofpolymerizable groups include hydroxy, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,isocyanato, aziridine, allyloxycarbonyloxy, and epoxy, e.g.,oxiranylmethyl. In other non-limiting embodiments, P may have astructure having a plurality of reactive groups, such as the reactivegroups disclosed herein. For example, in certain non-limitingembodiments, P may have a structure having from 2 to 4 reactive groups,as described herein. In certain non-limiting embodiment, having multiplereactive groups on P may allow for more effective incorporation into apolymer or allow for cross-linking between individual polymer strands.Suitable non-limiting examples of P groups with multiple reactive groupsinclude diacryloyloxy(C₁-C₁₈)alkyl; diacryloyloxyaryl;triacryloyloxy(C₁-C₁₈)alkyl; triacryloyloxyaryl;tetraacryloyloxy(C₁-C₁₈)alkyl; tetraacryloyloxyaryl;dihydroxy(C₁-C₁₈)alkyl; trihydroxy(C₁-C₁₈)alkyl;tetrahydroxy(C₁-C₁₈)alkyl; diepoxy(C₁-C₁₈)alkyl; diepoxyaryl;triepoxy(C₁-C₁₈)alkyl; triepoxyaryl; tetraepoxy(C₁-C₁₈)alkyl;tetraepoxyaryl; diglycidyloxy(C₁-C₁₈)alkyl; diglycidyloxyaryl;triglycidyloxy(C₁-C₁₈)alkyl; triglycidyloxyaryl;tetraglycidyloxy(C₁-C₁₈)alkyl; and tetraglycidyloxyaryl.

Further, with reference to Formula I, each group Q may representhydroxy, amino, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy,silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,thioisocyanato, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylicester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkylaminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene, C₁-C₁₈alkyloxycarbonyloxy, or halocarbonyl. In certain non-limitingembodiments, the group Q may act as a reactive group such that a mesogencontaining compound comprising at least one group Q may be incorporatedinto the backbone of a polymer or copolymer. For example, Q may be apolymerizable group, such as those described herein, including a groupselected from hydroxy, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,isocyanato, thio, thioisocyanato, aziridine, allyloxycarbonyloxy,carboxylic acid or carboxylic acid derivative, and epoxy, e.g.,oxiranylmethyl. As used herein, the terms “(meth)acryloxy” and“(meth)acryloyloxy” are used interchangeably and refer to a substitutedor unsubstituted prop-2-en-1-oyloxy structure.

As described herein and with reference to Formula I, the groups L,(L)_(y) or (L)_(w) represents a linking group having a linear length offrom 1 to 500 atomic bonds. That is, for the general structure F-L-E,the longest linear length of the linking group between groups F and E(where groups F and E may each generally represent any of groups P, R,Q, X or a mesogen) ranges from 1 to 500 bonds (inclusive of theintervening atoms). It should be understood that when discussing thelinear length of the linking group, one of ordinary skill in the artwill understand that the length of the linking group may be calculatedby determining the length of each of the bonds in the linear sequenceand the distance occupied by the various intervening atoms in the linearsequence of the linking group and totaling the values. In certainnon-limiting embodiments, the longest linear sequence of bonds may be atleast 25 bonds between the linked groups. In other non-limitingembodiments, the longest linear sequence of bonds may be at least 30bonds. In still other non-limiting embodiments, the longest linearsequence of bonds may be at least 50 bonds. It has been determined that,in certain non-limiting embodiments, a linking group L with at least 25bonds improves a variety of benefits for the resulting mesogencontaining compound. For example, a linking group of at least 25 bondsmay improve the solubilities of the additives, such as the photochromiccompounds in compositions comprising the mesogen containing compounds;may provide for faster or improved alignment properties of thecompositions comprising the mesogen containing compounds; and/or maylower the viscosity of a composition comprising the mesogen containingcompound.

Each group L may be independently chosen for each occurrence, the sameor different, from a single bond, a polysubstituted, monosubstituted,unsubstituted or branched spacer independently chosen from aryl,(C₁-C₃₀)alkyl, (C₁-C₃₀)alkylcarbonyloxy, (C₁-C₃₀)alkylamino,(C₁-C₃₀)alkoxy, (C₁-C₃₀)perfluoroalkyl, (C₁-C₃₀)perfluoroalkoxy,(C₁-C₃₀)alkylsilyl, (C₁-C₃₀)dialkylsiloxyl, (C₁-C₃₀)alkylcarbonyl,(C₁-C₃₀)alkoxycarbonyl, (C₁-C₃₀)alkylcarbonylamino,(C₁-C₃₀)alkylaminocarbonyl, (C₁-C₃₀)alkyloxycarbonyloxy,(C₁-C₃₀)alkylaminocarbonyloxy, (C₁-C₃₀)alkylaminocarbonylamino,(C₁-C₃₀)alkylurea, (C₁-C₃₀)alkylthiocarbonylamino,(C₁-C₃₀)alkylaminocarbonylthio, (C₂-C₃₀)alkenyl, (C₁-C₃₀)thioalkyl,(C₁-C₃₀)alkylsulfonyl, (C₁-C₃₀)alkylsulfinyl, or(C₁-C₃₀)alkylsulfoyloxy, wherein each substituent is independentlychosen from (C₁-C₁₈)alkyl, (C₁-C₁₈)alkoxy, fluoro, chloro, bromo, cyano,(C₁-C₁₈)alkanoate ester, isocyanato, thioisocyanato, or phenyl.According to the various non-limiting embodiments, “w” may berepresented by an integer from 1 to 26, “y” may be represented by aninteger from 2 to 25, and “z” is either 1 or 2. It should be noted thatwhen more than one L group occurs in sequence, for example in thestructure (L)_(y) or (L)w where “y” and/or “w” is an integer greaterthan 1, then the adjacent L groups may or may not have the samestructure. That is, for example, in a linking group having the structure-(L)₃- or -L-L-L- (i.e., where “y” or “w” is 3), each group -L- may beindependently chosen from any of the groups L recited above and theadjacent -L- groups may or may not have the same structure. For example,in one exemplary non-limiting embodiment, -L-L-L- may represent—(C₁-C₃₀)alkyl-(C₁-C₃₀)alkyl-(C₁-C₃₀)alkyl- (i.e., where each occurrenceof -L- is represented by (C₁-C₃₀)alkyl, where each adjacent(C₁-C₃₀)alkyl group may have the same or different number of carbons inthe alkyl group). In another exemplary non-limiting embodiment, -L-L-L-may represent -aryl-(C₁-C₃₀)alkylsilyl-(C₁-C₃₀)alkoxy- (i.e., where eachoccurrence of -L- differs from the adjacent groups -L-). Thus, thestructure of (L)_(y) or (L)_(w) should be understood as covering allpossible combinations of the various sequences of the linking groups-L-, including those where some or all of the adjacent -L- groups arethe same and where all the adjacent -L- groups are different.

Still with reference to Formula I, the group R represents an end groupand may be selected from hydrogen, C₁-C₁₈ alkyl, C₁-C₁₈alkoxy, C₁-C₁₈alkoxycarbonyl, C₃-C₁₀cycloalkyl, C₃-C₁₀cycloalkoxy, poly(C₁-C₁₈alkoxy),or a straight-chain or branched C₁-C₁₈alkyl group that is unsubstitutedor substituted with cyano, fluoro, chloro, bromo, or C₁-C₁₈ alkoxy, orpoly-substituted with fluoro, chloro, or bromo.

As noted herein, at least one of the first liquid crystal monomer of thematrix phase and the at least one liquid crystal material of the guestphase may have a structure according to Formula I. That is, in onenon-limiting embodiment, the first liquid crystal monomer of the matrixphase may have a structure according to Formula I and the structure ofthe at least one liquid crystal material of the guest phase may beanother liquid crystal material, such as a commercially available liquidcrystal material. Alternatively, in another non-limiting embodiment, thefirst liquid crystal monomer of the matrix phase may be another liquidcrystal monomer, such as a commercially available liquid crystalmonomer, and the structure of the at least one liquid crystal materialof the guest phase may have a structure according to Formula I. In stillanother non-limiting embodiment, both the first liquid crystal monomerof the matrix phase and the liquid crystal material of the guest phasemay have structures represented by Formula I, however, in thesenon-limiting embodiments, the structures of the compounds will not bethe same. That is, while both the structure of the first liquid crystalmonomer and the liquid crystal material may be generally represented byFormula I, the molecular structure of the first liquid crystal monomerwill be different that the molecular structure of the liquid crystalmaterial.

With further reference to Formula I, in certain non-limiting embodimentsthe groups Mesogen-1 and Mesogen-2 are each independently a rigidstraight rod-like liquid crystal group, a rigid bent rod-like liquidcrystal, or a rigid disc-like liquid crystal group. The structures forMesogen-1 and Mesogen-2 may be any suitable mesogenic group known in theart, for example, but not limited to, any of those recited in Demus etal., “Flüssige Kristalle in Tabellen,” VEB Deutscher Verlag fürGrundstoffundustrie, Leipzig, 1974 or “Flüssige Kristalle in TabellenII,” VEB Deutscher Verlag für Grundstoffundustrie, Leipzig, 1984.Further, according to certain non-limiting embodiments, the groupsMesogen-1 and Mesogen-2 may independently have a structure representedby:—[S¹]_(c)-[G¹ —[S²]_(d)]_(d′)-[G² —[S³]_(e)]_(e′)-[G³—[S⁴]_(f)]_(f′)—S⁵—In certain non-limiting embodiments, the mesogen structure, above, isfurther defined such that each group each G¹, G², and G³ mayindependently be chosen for each occurrence from: a divalent groupchosen from: an unsubstituted or a substituted aromatic group, anunsubstituted or a substituted alicyclic group, an unsubstituted or asubstituted heterocyclic group, and mixtures thereof, whereinsubstituents are chosen from: the group P, halogen, C₁-C₁₈alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl, C₁-C₁₈alkyloxycarbonyloxy,aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkylamino,di-(perfluoro(C₁-C₁₈)alkyl)amino, C₁-C₁₈ acetyl, C₃-C₁₀cycloalkyl,C₃-C₁₀cycloalkoxy, a straight-chain or branched C₁-C₁₈alkyl group thatis mono-substituted with cyano, halo, or C₁-C₁₈ alkoxy, orpoly-substituted with halo, and a group comprising one of the followingformulae: -M(T)_((t-1)) and -M(OT)_((t-1)), wherein M is chosen fromaluminum, antimony, tantalum, titanium, zirconium and silicon, T ischosen from organofunctional radicals, organofunctional hydrocarbonradicals, aliphatic hydrocarbon radicals and aromatic hydrocarbonradicals, and t is the valence of M. Further, in the mesogenicstructure, “c”, “d”, “e”, and “f” may be each independently chosen froman integer ranging from 0 to 20, inclusive and “d′”, “e′” and “f′” areeach independently an integer from 0 to 4 provided that a sum ofd′+e′+f′ is at least 1. Still with reference to the mesogenic structureabove, the groups S represent spacer groups such that each of groups S¹,S², S³, S⁴, and S⁵ may be independently chosen for each occurrence froma spacer unit chosen from:

-   -   (A) —(CH₂)_(g)—, —(CF₂)_(h)—, —Si(CH₂)_(g)—, or        —(Si(CH₃)₂O)_(h)—, wherein “g” is independently chosen for each        occurrence from 1 to 20 and “h” is a whole number from 1 to 16        inclusive;    -   (B) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)₂—C(Z′)₂—, or a single        bond, wherein Z is independently chosen for each occurrence from        hydrogen, C₁-C₁₈ alkyl, C₃-C₁₀cycloalkyl and aryl, and Z′ is        independently chosen for each occurrence from C₁-C₁₈ alkyl,        C₃-C₁₀ cycloalkyl and aryl; or    -   (C) —O—, —C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—,        —(O)S(O)O—, —O(O)S(O)O— or straight-chain or branched C₁-C₂₄        alkylene residue, said C₁-C₂₄ alkylene residue being        unsubstituted, mono-substituted by cyano or halo, or        poly-substituted by halo;        provided that when two spacer units comprising heteroatoms are        linked together the spacer units are linked so that heteroatoms        are not directly linked to each other and when S₁ and S₅ are        linked to another group, they are linked so that two heteroatoms        are not directly linked to each other.

According to specific non-limiting embodiments disclosed herein, in thestructure of the mesogen, above, “c”, “d”, “e”, and “f” each can beindependently chosen from an integer ranging from 1 to 20, inclusive;and “d′”, “e′” and “f′” each can be independently chosen from 0, 1, 2,3, and 4, provided that the sum of d′+e′+f′ is at least 1. According toother non-limiting embodiments disclosed herein, “c”, “d”, “e”, and “f”each can be independently chosen from an integer ranging from 0 to 20,inclusive; and “d′”, “e′” and “f′” each can be independently chosen from0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is at least 2.According to still other non-limiting embodiments disclosed herein, “c”,“d”, “e”, and “f” each can be independently chosen from an integerranging from 0 to 20, inclusive; and “d′”, “e′” and “f′” each can beindependently chosen from 0, 1, 2, 3, and 4, provided that the sum ofd′+e′+f′ is at least 3. According to still other non-limitingembodiments disclosed herein, “c”, “d”, “e”, and “f” each can beindependently chosen from an integer ranging from 0 to 20, inclusive;and “d′”, “e′” and “f′” each can be independently chosen from 0, 1, 2,3, and 4, provided that the sum of d′+e′+f′ is at least 1.

Finally, with reference to Formula I, the structure of the mesogencontaining compound in the various non-limiting embodiments of thepresent disclosure requires that:

-   -   when the group X is represented by —R, then “w” is an integer        from 1 to 25 and “z” is 1;    -   when the group X is represented by -(L)_(y)-R, then “w” is 1,        “y” is an integer from 2 to 25, and “z” is 1;    -   when the group X is represented by -(L)-R, then “w” is an        integer from 3 to 26 and “z” is 2;    -   when the group X is represented by -(L)_(w)-Q, then if the group        P in Formula I is represented by the group Q, which may be the        same or different than the other group Q, “w” is 1, and “z” is 1        and if the group P is other than the group Q (i.e., P is another        group as defined herein), then each “w” is independently an        integer from 1 to 26 and “z” is 1;    -   when the group X is represented by the structure

-   -    then “w” is 1, “y” is an integer from 2 to 25, and “z” is 1;    -   when the group X is represented by -(L)_(y)-P, then “w” is 1,        “y” is an integer from 2 to 26, and “z” is 1, and -(L)_(y)-        comprises a linear sequence of at least 25 bonds between the        mesogen and P; and    -   when the group X is represented by -(L)_(w)-[(L)_(w)-P]_(y),        then each “w” is independently an integer from 1 to 25, “y” is        an integer from 2 to 6, and “z” is 1.

According to certain non-limiting embodiments of the mesogen containingcompound, the mesogen containing compound may be a functionalmono-mesogen containing compound (i.e., a mesogen containing compoundthat contains one mesogenic structure). According to one non-limitingembodiment, the functional mono-mesogen containing compound may have astructure represented by Formula I, wherein the group X is representedby —R, “w” is an integer from 1 to 25, and “z” is 1. According toanother non-limiting embodiment, the functional mono-mesogen containingcompound may have a structure represented by Formula I, wherein thegroup X is represented by -(L)_(y)-R, “w” is 1, “y” is an integer from 2to 25, and “z” is 1.

According to other non-limiting embodiments of the mesogen containingcompound, the mesogen containing compound may be a functional bi-mesogencontaining compound (i.e., a mesogen containing compound that containstwo mesogenic structures (which may be the same or different)). For thevarious non-limiting embodiments, the structures of the functionalbi-mesogen containing compound will have a long chain linking groupbetween the two mesogenic units. According to one non-limitingembodiment, the functional bi-mesogen containing compound may have astructure represented by Formula I, wherein the group X is representedby -(L)-R, “w” is an integer from 3 to 26, and “z” is 2. According toanother non-limiting embodiment, the functional bi-mesogen containingcompound may have a structure represented by Formula I, wherein thegroup X is represented by

“w” is 1, “y” is an integer from 2 to 25, and “z” is 1.

In another non-limiting embodiment of the mesogen containing compound,the mesogen containing compound may be a functional mono-mesogencontaining compound (i.e., a mesogen containing compound that containsone mesogenic structure). According to specific non-limitingembodiments, the functional mono-mesogen containing compound may have astructure represented by Formula I, wherein the group X is representedby -(L)_(w)-Q and if the group P in Formula I is represented by thegroup Q, which may be the same or different than the other group Q, “w”is 1, and “z” is 1 and if the group P is other than the group Q, theneach “w” is independently and integer from 1 to 26 and “z” is 1.According to specific non-limiting embodiments, the structure of thisembodiment may contain two groups Q which may be the same or differentand may be reactive with one or more other monomeric units which mayreact to form a copolymer. According to these non-limiting embodiments,the mesogen containing compound may be a di-functional monomer that maybe incorporated into a polymer backbone, for example a polymer backbonein the guest phase. That is, the mesogen containing group will beincorporated into the polymer backbone and be attached at each end tothe formed polymer by the residues of the group(s) Q. In anothernon-limiting embodiment, the functional mono-mesogen containing compoundmay have a structure represented by Formula I, wherein the group X isrepresented by the -(L)_(y)-P, “w” is 1, “y” is an integer from 2 to 25,and “z” is 1; and -(L)_(y)-comprises a linear sequence of at least 25bonds between the mesogen and P. In specific non-limiting embodiments,-(L)_(y)- may comprise a linear sequence of at least 50 bonds betweenthe mesogen and P. In another non-limiting embodiment, the mesogencontaining compound may have a structure according to Formula I whereinthe group X is represented by the structure -(L)_(w)-[(L)_(w)-P]_(y),each “w” is independently an integer from 1 to 25, “y” is an integerfrom 2 to 6, and “z” is 1. According to these embodiments, the mesogencontaining compound may have from 3 to 7 reactive groups P.

Other non-limiting embodiments of suitable liquid crystal monomers forthe matrix phase or liquid crystal materials for the guest phase includematerials having a structure represented by Formula III:

where R, Mesogen-1, L, and Q are as defined herein.

According to various non-limiting embodiments, the at least partiallycured matrix phase may comprise a polymeric residue of at least a firstliquid crystal monomer. According to these embodiments, the at leastfirst liquid crystal monomer may be any of the liquid crystal monomersdescribed herein with reference to a matrix phase of a phase-separatedpolymer. At least partially curing the matrix phase may include at leastpartially polymerizing the at least first liquid crystal monomer of thematrix phase as described herein. For example, at least a portion of thefirst liquid crystal monomer of the matrix phase can be at leastpartially polymerized and thereby separated from at least a portion ofthe at least one photoactive material and the at least one liquidcrystal material of the guest phase to produce a matrix phase comprisingthe polymeric residue of at least the first liquid crystal monomer.Non-limiting methods of polymerization that can be used in conjunctionwith various non-limiting embodiments disclosed herein includephoto-induced polymerization and thermally-induced polymerization.

According to specific non-limiting embodiments of the phase-separatingpolymer system of the present disclosure, the at least one liquidcrystal material of the guest phase may comprise at least one secondliquid crystal monomer. According to certain non-limiting embodimentswhere the at least one liquid crystal material comprises at least onesecond liquid crystal monomer, the at least one second liquid crystalmonomer may be at least partially polymerized. In these non-limitingembodiments, the guest phase may comprise a residue of at least onesecond liquid crystal monomer, such that the guest phase is an at leastpartially cured guest phase. Specific non-limiting examples of the atleast second liquid crystal monomer may comprise a liquid crystalmonomer such as at least one mesogen containing compound represented byFormulae I or III. Other suitable liquid crystal monomers for the atleast second liquid crystal monomer include the other liquid crystalmonomers that are described or referenced elsewhere in this disclosure.

In specific non-limiting embodiments, the at least one second liquidcrystal monomer may be different from the first liquid crystal monomer.For example, in certain non-limiting embodiments, the at least onesecond liquid crystal monomer may be a liquid crystal monomer thatpolymerizes at a different polymerization rate than the at least onefirst liquid crystal monomer, such as, for example at a fasterpolymerization rate or a slower polymerization rate compared to thepolymerization rate of the at least one first liquid crystal monomer.Alternatively or in addition, the at least one second liquid crystalmonomer of the guest phase may polymerize via a different polymerizationinitiation method or polymerization mechanism than the at least onefirst liquid crystal monomer of the matrix phase. For example, butnot-limiting herein, at least one second liquid crystal monomer maypolymerize by a thermal initiation and the at least one first liquidcrystal monomer may polymerize by initiation by UV irradiation; or theat least one second liquid crystal monomer may polymerize by a freeradical addition mechanism and the at least one first liquid crystalmonomer may polymerize by a condensation mechanism. One having ordinaryskill in the art will recognize that other initiation methods orpolymerization mechanisms for the first liquid crystal monomer(s) andthe second liquid crystal monomer(s) may be used in various non-limitingembodiments of the present disclosure and such methods and mechanismsare to be considered as being included in the present disclosure.

Specific non-limiting embodiments of the phase-separating polymer systemcomprise a guest phase comprising an at least second liquid crystalmonomer, wherein the guest phase may at least partially cure at adifferent rate than the matrix phase. For example, according to onenon-limiting embodiment, the guest phase may at least partially cure ata rate that is slower than the rate at which the matrix phase at leastpartially cures. According to another non-limiting embodiment, the guestphase may at least partially cure at a rate that is faster than the rateat which the matrix phase at least partially cures.

According to certain non-limiting embodiments, the phase-separatingpolymer system may comprise an at least second crystal monomer, wherethe at least second liquid crystal monomer may polymerize by a differentinitiation method than the at least first liquid crystal. Thereforeaccording to this non-limiting embodiment, the guest phase may at leastpartially cure by a different polymerization initiation method than thematrix phase. In other non-limiting embodiments, the phase-separatingpolymer system may comprise an at least second crystal monomer, wherethe at least second liquid crystal monomer may polymerize by a differentpolymerization mechanism than the at least first liquid crystal.Therefore according to this non-limiting embodiment, the guest phase mayat least partially cure by a different polymerization mechanism than thematrix phase.

According to various non-limiting embodiments of the phase-separatingpolymer system, the guest phase, for example, the uncured guest phase orthe at least partially cured guest phase may have a lower Fischermicrohardness compared to the at least partially cured matrix phase.Fischer microhardness, as used herein, is a measurement of the hardness(or softness) of system, a polymer, phase, or polymerized phase, suchas, for example, the uncured or at least partially cured guest phase orthe at least partially cured matrix phase. It is believed that theincreased flexibility in the structure of the at least one liquidcrystal material, for example, the mesogen containing compoundsdisclosed herein may impart certain desirable characteristics to acomposition such as the guest phase or the at least partially curedguest phase. For example, while not wishing to be limited by anyinterpretation, it is believed that flexibility, such as flexibility inthe at least one liquid crystal material, for example, in the one ormore linking group “L” in the mesogen containing compound according toFormulae I and III or residue thereof, may result in a guest phase orthe at least partially cured guest phase having a “softer” structure. Asused herein, with reference to the character of one or more of thephases (including both uncured and at least partially cured phases) ofthe phase-separated polymer systems described herein, the term “softer”refers to compositions exhibiting a Fischer microhardness typically lessthan 150 Newtons/mm², e.g., from 0 to 149.9 Newtons/mm². Cured phases ofthe phase-separating polymer system having a softer structure maydisplay desired or improved characteristics, for example, improvedliquid crystal character, improved photochromic performance, improveddichroic performance, and/or improved photochromic-dichroic performance.For example, for uncured phases and at least partially cured phases suchas a liquid crystal polymer, a liquid crystal copolymer or blends ofliquid crystal (co)polymers, it may be desirable to have hard and/orsoft segments or components in the polymer. The concept that curedpolymers may be composed of hard and soft segments or components isknown in the art (see, for example, “Structure-Property-Relationship inPolyurethanes”, Polyurethane Handbook, G. Oertel, editor, 2nd ed. HanserPublishers, 1994, pp 37-53, incorporated by reference herein). Thus, forexample herein, a hard phase, segment or component may include a morecrystalline or semi-crystalline region within the at least partiallycured polymer structure or phase, whereas a soft phase, segment orcomponent includes a more amorphous, non-crystalline or rubbery region.In certain non-limiting embodiments, the contribution of the structureof a component, material, monomer or monomer residue in a phase toeither the hardness or softness of the resulting phase, such as theguest phase or the matrix phase, may be determined, for example, bymeasuring the Fischer microhardness of a cured polymer comprisingcomponent, material, monomer or monomer residue. The physical propertiesof the phases are derived from their molecular structure and aredetermined by the choice of building blocks, e.g., the choice ofmaterials, monomers, the at least first liquid crystal monomer, the atleast second liquid crystal monomer, and other reactants, additives, theratio of hard and soft segments, and the supramolecular structurescaused by atomic interactions between materials and/or polymer chains.Materials and methods for the preparation of polymers, for example,polyurethanes, are described in Ullmann's Encyclopedia of IndustrialChemistry, 5th ed., 1992, Vol. A21, pages 665-716, which description isincorporated by reference herein.

For example, in the photochromic, dichroic, and/or photochromic-dichroiccompounds and cured phases, layers, and coatings described herein, it isbelieved that the soft segments or components of the phases in thelayers and coatings, including cured layers and coatings, may provide animproved solubilizing environment for the photochromic,photochromic-dichroic, and/or dichroic compound(s) to reversiblytransform from a first state to a second state, while the hard segmentsor components of the phases, such as the matrix phase, or coatingprovides structural integrity for the material or coating and/or preventmigration of the transformable compounds. In one non-limitingapplication for photochromic, dichroic and/or photochromic-dichroiccompound(s), a balance of soft and hard materials in one or more phasesmay achieve desired benefits of a suitable cured material or cured layeror coating, i.e., a material, layer, or coating having a phase with aFischer microhardness ranging from 0 to 150 Newtons/mm² that alsoexhibits good photochromic, dichroic and/or photochromic-dichroicresponse characteristics. In another non-limiting application, thephotochromic, dichroic and/or photochromic-dichroic compound(s) may belocated in a guest phase, such as an uncured or at least partially curedguest phase having a Fischer microhardness less than 60 Newtons/mm²,e.g. from 0 to 59.9 Newtons/mm², or alternatively from 5 to 25Newtons/mm², which may be included in a matrix phase comprising one ormore harder polymeric material to provides structural strength. In afurther non-limiting application, the photochromic, dichroic and/orphotochromic-dichroic compound(s) may be within a soft polymeric guestphase incorporated in a hard polymeric matrix phase coating or material,e.g., a matrix phase having a Fischer microhardness greater than 150Newtons/mm², e.g. from 150 to 200 Newtons/mm² or even higher.

According to other non-limiting embodiments of phase-separating polymersystems disclosed herein, it may be desirable to have an at leastpartially cured matrix phase that is softer than an at least partiallycured guest phase. For example, according to certain non-limitingembodiments, the present disclosure may provide a switchable liquidcrystal cell comprising a soft matrix phase and a harder guest phase.Thus, according to these non-limiting embodiments, the phase-separatingpolymer system may comprise an at least partially cured guest phasehaving a higher Fischer microhardness compared to the at least partiallycured matrix phase. Non-limiting examples of hard (i.e., high) Fischermicrohardness values and soft (i.e., low) Fischer microhardness are setforth above. According to these non-limiting embodiments, the at leastone photoactive material may selectively concentrate in the matrix phaseupon phase separation. The at least one photoactive material may displayimproved photochromic and/or dichroic properties in the matrix phasecompared to a photoactive material in a harder guest phase.

According to certain non-limiting embodiments of the phase-separatingpolymer systems, the at least one photoactive material may be adapted toswitch from a first state to a second state in response to at leastactinic radiation and to revert back to the first state in response tothermal energy. For example, in those non-limiting embodiments where theat least one photoactive material is selected from photochromiccompounds or photochromic-dichroic compounds, the at least onephotoactive material may switch from a first non-colored or clear stateto a second colored state in response to at least actinic radiation andrevert back to the non-colored/clear state from the colored state inresponse to thermal energy. In other non-limiting embodiments where theat least one photoactive material is selected from dichroic compounds orphotochromic-dichroic compounds, the at least one photoactive materialmay switch from a first non-polarized state to a second polarized statein response to at least actinic radiation and revert back to thenon-polarized state from the polarized state in response to thermalenergy. In other non-limiting embodiments of the dichroic compounds orphotochromic-dichroic compounds, the first state may be a polarizedstate and the second state may be a non-polarized state. In still othernon-limiting embodiments, both the first and second states of thedichroic compounds or photochromic-dichroic compounds may be polarizing,for example, polarizing in the same general direction in both states orin other non-limiting embodiments, may polarize radiation in differentdirections in one state compared to the other. In specific non-limitingembodiments of the phase-separating polymer systems described herein,the at least one photoactive material may have improved performancecharacteristics when incorporated into the guest phase than aphotoactive material in the at least partially cured matrix phase. Onenon-limiting example of an improved performance characteristic of thephotoactive material is faster kinetics. As used herein the term “fasterkinetics” when used in reference to a photoactive material, such as aphotochromic compound, a dichroic compound, or photochromic-dichroiccompound capable of transitioning for a first state to a second state inresponse to absorption of at least actinic radiation and transitioningfrom the second state back to the first state in response to thermalenergy, means that the kinetic rate of at least one of the transitionfrom the first state to the second state or the transition from thesecond state back to the first state is faster (i.e., the transitiontakes a shorter amount of time), as measured by the T ½, for aphotoactive material in a first environment, such as the guest phase,compared to the photoactive material in a second environment, such asthe matrix phase. As used herein the term “T½” is a measurement of theamount of time necessary for the optical density of a photoactivematerial to fade to a value of one half of its activated value.

According to other non-limiting embodiments of the phase-separatingpolymer systems of the present disclosure, at least a portion of atleast one of the polymeric residue of at least the first liquid crystalmonomer of the at least partially cured matrix phase and the at leastone liquid crystal material of the guest phase, for example in theuncured guest phase or the at least partially cured guest phase, may beat least partially ordered. According to these non-limiting embodiments,at least a portion of the polymeric residue of at least the first liquidcrystal monomer of the at least partially cured matrix phase and atleast a portion of the at least one liquid crystal material of the guestphase may be at least partially ordered such that the at least partiallyordered portion of the polymeric residue of at least the first liquidcrystal monomer has a first general direction and the at least partiallyordered portion of the at least one liquid crystal material of the guestphase has a second generally direction that is generally parallel to thefirst general direction. As set forth in detail elsewhere herein, incertain non-limiting embodiments, at least a portion of the polymericresidue of at least the first liquid crystal monomer of the matrix phaseand at least a portion of the at least one liquid crystal material ofthe guest phase may be at least partially ordered prior to at leastpartially curing at least a portion of the matrix phase oralternatively, the polymeric residue of at least the first liquidcrystal monomer of the matrix phase and at least a portion of the atleast one liquid crystal material of the guest phase may be at leastpartially ordered subsequent to at least partially curing at least aportion of the matrix phase and even, according to specific non-limitingembodiments, after at least partially curing at least a portion of theguest phase. Methods for at least partially ordering the polymericresidue of at least the first liquid crystal monomer of the matrix phase(which may in certain non-limiting embodiments be an at least partiallycured matrix phase) and at least a portion of the at least one liquidcrystal material of the guest phase (which may in certain non-limitingembodiments be an at least partially cured guest phase) are set forth indetail herein and include, but are not limited to, exposing the liquidcrystal materials or monomers (or residues of monomers) to at least oneof a magnetic field, an electric field, linearly polarized infraredradiation, linearly polarized ultraviolet radiation, linearly polarizedvisible radiation, and shear force. Other non-limiting embodiments of atleast partially ordering at least a portion of the liquid crystalmaterials or monomers (or residues of monomers) of the phases mayinclude the use of an alignment facility or alignment material, such asdescribed in detail herein.

According to further non-limiting embodiments of the phase-separatingpolymer systems described herein, at least one of the at least partiallycured matrix phase and the guest phase may further comprise one or moreadditive selected from a liquid crystal, a liquid crystal controladditive, a non-linear optical material, a dye, a dichroic dye (such asthose described herein), an alignment promoter, a kinetic enhancer, aphotoinitiator, a thermal initiator, a surfactant, a polymerizationinhibitor, a solvent, a light stabilizer, a heat stabilizer, a moldrelease agent, a rheology control agent, a leveling agent, a freeradical scavenger, a coupling agent, a tilt control additive, a block ornon-block polymeric material or an adhesion promoter. Non-limitingexamples of the one or more additives are described in detail in U.S.application Ser. No. 12/163,180, filed Jun. 27, 2008, entitled“Formulations Comprising Mesogen Containing Compounds” at paragraphs[0085]-[0105], which disclosure is incorporated by reference herein.

Still other non-limiting embodiments of the present disclosure providefor optical elements. According to various non-limiting embodiments, theoptical elements may comprise a substrate and an at least partial layeror coating on at least a portion of the substrate, where the layercomprises a phase-separating polymer system, such as a liquid crystalphase-separating system, as set forth herein. As used herein the term“layer” includes layers, coatings, and films, which may be at leastpartially cured. According to certain non-limiting embodiments of theoptical elements, the liquid crystal phase-separating polymer system maycomprise an at least partially cured matrix phase comprising a polymericresidue of at least a first liquid crystal monomer, and a guest phasecomprising at least one photoactive material selected from photochromiccompounds, dichroic compounds, or photochromic-dichroic compounds and atleast one liquid crystal material. At least a portion of the guest phasemay separate from at least a portion of the matrix phase during the atleast partial curing of the polymeric residue of at least the firstliquid crystal monomer. Non-limiting examples of the phase-separatingpolymer systems are described in detail herein. For example, in onenon-limiting embodiment, at least one of the first liquid crystalmonomer of the matrix phase and the at least one liquid crystal materialof the guest phase may be a mesogen containing material having astructure represented by Formula I:

where potential structures of P, L, Mesogen-1, and X; ad values for “w”and “z” are set forth in detail herein, or a mesogen containing materialhaving a structure represented by Formula III, as set forth herein. Inother non-limiting embodiments, the first liquid crystal monomer of thematrix phase and/or the liquid crystal material of the matrix phase maycomprise commercially available or known liquid crystal monomer orliquid crystal materials. Examples of optical elements include, but arenot limited to, elements or devices chosen from ophthalmic elements anddevices, display elements and devices, windows, mirrors, and active andpassive liquid crystal cell elements and devices.

Generally speaking, substrates that are suitable for use in conjunctionwith various non-limiting embodiments of the optical elements disclosedherein include, but are not limited to, substrates formed from organicmaterials, inorganic materials, or combinations thereof (for example,composite materials). Non-limiting examples and detailed descriptions ofsubstrates that can be used in accordance with various non-limitingembodiments disclosed herein are described in more detail in U.S.application Ser. No. 12/163,180, filed Jun. 27, 2008, entitled“Formulations Comprising Mesogen Containing Compounds” at paragraphs[0134]-[0143], which disclosure is incorporated by reference herein.

In specific non-limiting embodiments of the optical elements, at least aportion of the polymeric residue of the at least first liquid crystalmonomer of the at least partially cured matrix phase and at least aportion of the at least one liquid crystal material of the guest phaseare at least partially ordered. The various non-limiting embodiments maybe at least partially ordered such that the at least partially orderedportion of the polymeric residue of the at least first liquid crystalmonomer of the at least partially cured matrix phase has a first generaldirection and the at least partially ordered portion of the at least oneliquid crystal material of the guest phase has a second generaldirection that is generally parallel to the first general direction.Methods of at least partially ordering the liquid crystal materials andmonomers (including residues of monomers) of the phases are described indetail herein.

In specific non-limiting embodiments of the optical elements, the atleast one liquid crystal material of the guest phase may comprise aresidue of at least one second liquid crystal monomer, which may be atleast partially polymerized such that the guest phase is an at leastpartially cured guest phase. As described herein, in certainnon-limiting embodiments, the at least one second liquid crystal monomerof guest phase may polymerize at a different rate, such as a slower rateor a faster rate, than the at least first liquid crystal monomer of thematrix phase. For example, the at least one second liquid crystalmonomer of guest phase may polymerize by a different initiation methodor a different polymerization mechanism than the at least first liquidcrystal monomer of the matrix phase. Thus, according to one non-limitingembodiments the at least a portion of the guest phase may cure at aslower rate than the at least a portion of the matrix phase andaccording to another non-limiting embodiments the at least a portion ofthe guest phase may cure at a faster rate than the at least a portion ofthe matrix phase.

According to other non-limiting embodiments, the at least partial layeron at least a portion of a surface of the substrate may be adapted toswitch from a first state to a second state in response to at leastactinic radiation and to revert back to the first state in response tothermal energy. As discussed in detail herein, the at least partiallayer comprises a liquid crystal phase-separated system comprising aguest phase with at least one photoactive material therein. The at leastone photoactive material may be selected from photochromic compounds,dichroic compounds, and photochromic-dichroic compounds, each of whichmay be adapted to switch from a first state to a second state inresponse to at least actinic radiation and revert back to the firststate in response to thermal energy. In other non-limiting embodiments,the at least partial layer on at least a portion of a surface of thesubstrate may be adapted to linearly polarize at least transmittedradiation in at least one of the first state and the second state. Forexample, the at least one photoactive compound may comprise dichroiccompounds and/or photochromic-dichroic compound such that the at leastpartial layer may be adapted to linearly polarize at least transmittedradiation in at least one of the first state and the second state. Inother non-limiting embodiment, the at least partial layer may compriseone or more elements capable of linearly polarizing at least transmittedradiation one or both of the first and second states.

Further non-limiting embodiments of the optical elements may compriseone or more additional at least partial layers on at least a portion ofa surface the substrate, where the one or more additional layers may beselected from a tie layer, a primer layer, an abrasion resistantcoating, a hard coating, a protective coating, a reflective coating, aconventional photochromic coating, an anti-reflective coating, alinearly polarizing coating, a circularly polarizing coating, anelliptically polarizing coating, a transitional coating, or combinationsthereof. In certain non-limiting embodiments, one or more of theadditional at least partial layers may be coated onto the surface of thesubstrate prior to the at least partial layer comprising the liquidcrystal phase-separating system. That is, the one or more additional atleast partial layers may be between the substrate surface and the liquidcrystal phase-separating system layer. In other non-limitingembodiments, one or more of the additional at least partial layers maybe coated onto the substrate after to the at least partial layercomprising the liquid crystal phase-separating system. That is, the oneor more additional at least partial layers may be coated onto at least aportion of an outer surface of the liquid crystal phase-separatingsystem layer or alternatively on an outer surface of one or more otheradditional layers coated on the outer surface of the liquid crystalphase-separating system layer. In still other non-limiting embodiments,one or more of the additional layers may be on at least a differentportion of the substrate, for example on a different surface of thesubstrate than the liquid crystal phase-separating system layer, such asan opposite surface of the substrate. Non-limiting examples of the atleast one additional at least partial layers are described in detailherein and in U.S. application Ser. No. 12/163,180, filed Jun. 27, 2008,entitled “Formulations Comprising Mesogen Containing Compounds” atparagraphs [0144]-[0151], which disclosure is incorporated by referenceherein.

Still other non-limiting embodiments of the present disclosure providefor articles of manufacture comprising an at least partially curedmatrix phase comprising a polymeric residue of at least a first liquidcrystal monomer; and a guest phase comprising at least one photoactivematerial and at least one liquid crystal material, such as the liquidcrystal materials discussed herein, wherein at least a portion of theguest phase separates from at least a portion of the matrix phase duringthe at least partial curing of the polymeric residue of the first liquidcrystal monomer. The at least one photoactive material may be selectedfrom photochromic compounds, dichroic compounds, orphotochromic-dichroic compounds, as detailed herein. As set forthherein, the at least one liquid crystal material may be at least onesecond liquid crystal monomer or residue thereof, as described herein.In specific non-limiting embodiments, at least one of the first liquidcrystal monomer and the at least one liquid crystal monomer may compriseat least one mesogen containing compound having a structure representedby Formulae I or II, as described in detail herein. Non-limitingexamples of articles of manufacture include molded articles, assembledarticles and cast articles. For example, articles of manufacture, suchas, molded assembled, or cast articles for use in applications andvarious related devices, such as, but not limited to, use in opticaldata storage applications, as photomasks, as decorative pigments; incosmetics and for security applications (see, for example U.S. Pat. No.6,217,948, which disclosure is incorporated by reference herein); ascurable resins for medical, dental, adhesive and stereolithographicapplications (see, for example, U.S. Pat. No. 7,238,831, whichdisclosure is incorporated by reference herein).

Other non-limiting embodiments of the present disclosure provide methodsof forming the phase-separating polymer systems (such as the liquidcrystal phase-separating polymer systems), the optical elements, and thearticles of manufacture described herein. For example, according tocertain non-limiting embodiments, the present disclosure providesmethods for forming a liquid crystal phase-separating photochromic,dichroic, or photochromic-dichroic polymer system, which may beincorporated into an optical element or article of manufacture.According to these methods, forming a liquid crystal phase-separatingphotochromic, dichroic, or photochromic-dichroic polymer system maycomprise providing a phase-separating polymer forming compositioncomprising a matrix phase forming material, a guest phase formingmaterial and at least one photoactive material; at least partiallyordering at least a portion of the matrix phase forming material and atleast a portion of the guest phase forming material; causing at least aportion of the guest phase forming material to separate from at least aportion of the matrix phase forming material; and at least partiallycuring at least a portion of the matrix phase forming material toproduce an at least partially cured matrix phase.

According to non-limiting embodiments of these methods, the matrix phaseforming material may comprise at least a first liquid crystal monomer,such as described herein; the guest phase forming material may compriseat least one liquid crystal material, such as described herein, and theat least one photoactive material may be selected from photochromiccompounds, dichroic compounds, or photochromic-dichroic compounds, asdescribed herein.

According to these non-limiting embodiments, at least partially orderingat least a portion of the matrix phase forming material and at least aportion of the guest phase forming material may include at leastpartially ordering the at least first liquid crystal monomer of thematrix phase forming material and at least partially ordering the atleast one liquid crystal material of the guest phase forming materialsuch that the at least partially ordered portion of the at least firstliquid crystal monomer of the matrix phase forming material has a firstgeneral direction and the at least partially ordered portion of the atleast one liquid crystal material of the guest phase forming materialhas a second general direction that is generally parallel to the firstgeneral direction. In other non-limiting embodiments, the ordering stepmay further comprise at least partially ordering the at least onephotoactive material, for example, when the at least one photoactivematerial comprises dichroic compound(s) and/or photochromic-dichroiccompound(s), such that the at least one photoactive material has a thirdgeneral direction that is generally parallel to the first generaldirection and the second general direction. Methods of at leastpartially ordering at least a portion of the at least first liquidcrystal monomer of the matrix phase forming material, the at least aportion of the at least one liquid crystal material of the guest phaseforming material, and in certain non-limiting embodiments, the at leastone photoactive material are described in detail herein and may includeordering the materials by exposing at least a portion of the materialsto at least one of a magnetic field, an electric field, linearlypolarized infrared radiation, linearly polarized ultraviolet radiation,linearly polarized visible radiation, and shear force. Othernon-limiting embodiments of at least partially ordering at least aportion of the materials may include the use of an alignment facility oralignment material, as described in detail herein.

According to specific non-limiting embodiments of the methods, the atleast one liquid crystal material of the guest phase forming materialmay be chosen from a mesogen containing compound or a second liquidcrystal monomer. Non-limiting examples of mesogen containing compoundsand liquid crystal monomers that may be used in these non-limitingembodiments of the at least one liquid crystal material of the guestphase forming material are described in detail herein. In certainnon-limiting embodiments of the methods, the at least one liquid crystalmaterial of the guest phase forming material may comprise at least onemesogen containing compound having a structure represented by Formulae Iand III as set forth in detail herein. In other non-limiting embodimentsof the methods, the first liquid crystal monomer of the matrix phaseforming material may comprise at least one mesogen containing compoundhaving a structure represented by Formulae I and III as set forth indetail herein.

With reference to the method step of causing at least a portion of theguest phase forming material to separate from at least a portion of thematrix phase forming material, the separation of the at least a portionof the guest phase forming material from at least a portion of thematrix phase forming material may be affected by using one ofpolymerization induced phase-separation and solvent inducedphase-separation, as described herein. In one non-limiting embodiment,causing at least a portion of the guest phase forming material toseparate from at least a portion of the matrix phase forming materialmay cause the at least one photoactive material to selectivelyconcentrate in the guest phase forming material, such as those portionsof the guest phase forming material that has at least partiallyseparated from the matrix phase forming material. In other non-limitingembodiments, the at least one photoactive materials may selectivelyconcentrate in the matrix phase forming material, such that thoseportions of the matrix phase forming material that is at least partiallyseparated from the guest phase forming material. In still othernon-limiting embodiments, where the at least one photoactive materialscomprises two or more photoactive materials, some but not all of one (ormore) photoactive material(s) may selectively concentrate in the guestphase forming material, while a second (or more) photoactive material(s)may selectively concentrate in the matrix phase forming material oralternatively may be evenly dispersed in both the guest phase formingmaterial and the matrix phase forming material.

According to one non-limiting embodiment, causing the at least a portionof the guest phase forming material to separate from at least a portionof the matrix phase forming material may be affected by a polymerizationinduced phase-separation. For example, in one non-limiting embodiment,causing the at least a portion of the guest phase forming material toseparate from at least a portion of the matrix phase forming materialmay comprise at least partially polymerizing at least a portion of theat least first liquid crystal monomer of the matrix phase formingmaterial. As discussed herein, polymerizing (or curing) at least aportion of the guest phase forming material may result in the at leastone first liquid crystal monomer forming a residue of the at least onefirst liquid crystal monomer within the matrix phase. In anothernon-limiting embodiment wherein the at least one liquid crystal materialof the guest phase forming material comprises at least a second liquidcrystal monomer, causing the at least a portion of the guest phaseforming material to separate from at least a portion of the matrix phaseforming material may further comprise at least partially polymerizing atleast a portion of the at least second liquid crystal monomer of theguest phase forming material. In these non-limiting embodiments, atleast partially polymerizing at least a portion of the at least secondliquid crystal monomer may result in a polymeric residue of the secondliquid crystal monomer within at least a portion of the guest phase.

In other non-limiting embodiments where the method further comprises atleast partially polymerizing at least a portion of the guest phase aftercausing at least a portion of the guest phase forming material toseparate from at least a portion of the matrix phase forming material,the guest phase forming material may comprise a monomer that may bepolymerized at a different time or rate, for example, by a differentpolymerization initiation method or a different polymerizationmechanism, as described herein, than the at least first liquid crystalmonomer of the matrix phase forming material. In one non-limitingembodiment, the at least one liquid crystal material of the guest phaseforming material is at least one second liquid crystal monomer that maybe polymerized at a different time or rate, for example, by a differentpolymerization initiation method or a different polymerizationmechanism, as described herein, than the at least first liquid crystalmonomer of the matrix phase forming material. According to thesenon-limiting embodiments, the method comprises at least partiallypolymerizing (or curing) the guest forming material such as bypolymerizing the at least one second liquid crystal monomer or othermonomer in the guest phase forming material. In specific non-limitingembodiments, the guest phase forming material may comprise anothermonomer, such as a non-liquid crystal monomer that may be polymerized inthe guest phase after curing the matrix phase or during the curing ofthe matrix phase. In certain embodiments, at least partiallypolymerizing at least a portion of the guest phase forming material maybe affected after causing at least a portion of the guest phase formingmaterial to separate from at least a portion of the matrix phase formingmaterial by polymerization induced phase-separation. In otherembodiments, at least partially polymerizing at least a portion of theguest phase forming material may be affected after causing at least aportion of the guest phase forming material to separate from at least aportion of the matrix phase forming material by solvent inducedphase-separation.

In still further non-limiting embodiments of the methods, the methodsmay further comprise coating at least a portion of a surface of asubstrate with a liquid crystal phase-separating polymer system asdescribed herein, such as the liquid crystal phase-separatingphotochromic, dichroic, or photochromic-dichroic polymer system. Coatingat least a portion of a surface of the substrate may be done by avariety of methods known in the art, such as, but not limited to,imbibing, coating, overmolding, spin coating, spray coating, spray andspin coating, curtain coating, flow coating, dip coating, injectionmolding, casting, roll coating, spread coating, casting-coating, reverseroll-coating, transfer roll-coating, kiss/squeeze coating, gravureroll-coating, slot-die coating, blade coating, knife coating, androd/bar coating and wire coating. Various coating methods suitable foruse in certain non-limiting embodiments of the present disclosure aredescribed in “Coating Processes”, Kirk-Othmer Encyclopedia of ChemicalTechnology, Volume 7, pp 1-35, 2004. Methods of imbibition are describedin U.S. Pat. No. 6,433,043 at column 1, line 31 to column 13, line 54.The disclosure of each of these references is incorporated in theirentirety by this reference. According to certain non-limitingembodiments, the at least partially coated substrate may be part of anoptical element, such as described herein. In specific non-limitingembodiments, the optical element may be an ophthalmic element, such ascorrective and non-corrective lenses, including single vision ormulti-vision lenses, which may be either segmented or non-segmentedmulti-vision lenses (such as, but not limited to, bifocal lenses,trifocal lenses and progressive lenses), as well as other elements usedto correct, protect, or enhance (cosmetically or otherwise) vision,including without limitation, contact lenses, intra-ocular lenses,magnifying lenses, and protective lenses or visors; and may also includepartially formed lenses and lens blanks. In other non-limitingembodiments, the at least partially coated substrate may be incorporatedinto an article of manufacture, as described herein.

In other non-limiting embodiments of the methods, the phase-separatingpolymer compositions described herein may further comprise at least oneadditive selected from a liquid crystal, a liquid crystal controladditive, a non-linear optical material, a dye, an alignment promoter, akinetic enhancer, a photoinitiator, a thermal initiator, a surfactant, apolymerization inhibitor, a solvent, a light stabilizer, a heatstabilizer, a mold release agent, a rheology control agent, a levelingagent, a free radical scavenger, a coupling agent, a tilt controladditive, a block or non-block polymeric material, an adhesion promoteror combinations of any thereof. Examples of the at least one additiveare described elsewhere herein. According to various non-limitingembodiments, any particular compound in the at least one additive may befound primarily in the matrix phase of the phase-separating polymercomposition, primarily in the guest phase of the phase-separatingpolymer composition, or distributed approximately evenly through boththe matrix phase and guest phase of the phase-separating polymercomposition.

Further, according to the various non-limiting embodiments, the sheetcomprising a liquid crystal polymer and a liquid crystal materialdistributed therein can be connected to at least a portion of an opticalsubstrate by at least one of laminating, fusing, in-mold casting, andadhesively bonding at least a portion of the sheet to the opticalsubstrate.

Another non-limiting embodiment provides a method of making an alignmentfacility for an optical dye comprising forming an at least partialcoating comprising an interpenetrating polymer network on at least aportion of an optical substrate. As used herein the term“interpenetrating polymer network” means an entangled combination ofpolymers, at least one of which is cross-linked, that are not bonded toeach other. Thus, as used herein, the term interpenetrating polymernetwork includes semi-interpenetrating polymer networks. For example,see L. H. Sperling, Introduction to Physical Polymer Science, John Wiley& Sons, New York (1986) at page 46. According to this non-limitingembodiment, the method comprises imparting an orientation facility on atleast a portion of an optical substrate and applying a polymerizablecomposition and a liquid crystal material to the at least a portion ofthe orientation facility. Thereafter, at least a portion of the liquidcrystal material can be at least partially aligned with at least aportion of the orientation facility. After at least partially aligningat least a portion of the liquid crystal material, at least a portion ofthe at least partial coating can be subjected to a dual curing process,wherein at least a portion of the liquid crystal material is at leastpartially set and at least a portion of the polymerizable composition isat least partially set. According to this non-limiting embodiment, atleast partially setting at least a portion of the liquid crystalmaterial can occur before, after, or at essentially the same time as atleast partially setting the polymerizable composition.

For example, in one non-limiting embodiment at least a portion of theliquid crystal material of the interpenetrating polymer network can beexposed to ultraviolet radiation to at least partially set at least aportion of the liquid crystal material. Thereafter, at least a portionof the polymerizable composition can be at least partially set byexposure to thermal energy. Although not limiting herein, according tothis non-limiting embodiment, the polymerizable composition can comprisedihydroxy and isocyanate monomers, and a liquid crystal material cancomprise a liquid crystal monomer. As used herein, the term “thermalenergy” means any form of heat.

In another non-limiting embodiment, at least a portion of thepolymerizable composition can be exposed to thermal energy sufficient tocause at least a portion of the polymerizable composition to at leastpartially set prior to exposing at least a portion of the liquid crystalmaterial to ultraviolet radiation to cause at least a portion of theliquid crystal material to at least partially set. Further, at least aportion of the liquid crystal material can be at least partially alignedbefore, during or after exposing at least a portion of the coating tothermal energy and prior to at least partially setting at least aportion of the liquid crystal material.

In still another non-limiting embodiment, at least partially setting atleast a portion of the polymerizable composition can occur atessentially the same time as at least partially setting at least aportion of the liquid crystal material, for example, by simultaneouslyexposing the at least partial coating to UV and thermal energy.

Generally, the at least partial coatings comprising the interpenetratingpolymer network according to various non-limiting embodiments disclosedherein can have any thickness necessary to achieve the desired thicknessof the alignment facility. For example, although not limiting herein, inone non-limiting embodiment, the thickness of the at least partialcoating comprising the interpenetrating polymer network can range from 1to 100 microns. Further, according to various non-limiting embodimentsdisclosed herein, the polymerizable composition of the interpenetratingpolymer network can be an isotropic material or an anisotropic material,provided that the at least partial coating is, on the whole,anisotropic.

Optical elements according to various non-limiting embodiments will nowbe described. Referring now to FIG. 2, one non-limiting embodimentprovides an ophthalmic element, which is generally indicated 220,comprising an ophthalmic substrate 222 and an alignment facility(generally indicated 223) for an optical dye comprising at least one atleast partial coating 224 comprising an at least partially orderedliquid crystal material connected to at least a portion thereof. As usedherein the term “connected to” means in direct contact with an object orin indirect contact with an object through one or more other structuresor materials, at least one of which is in direct contact with theobject. Non-limiting methods of forming such alignment facilities areset forth above in detail. Further, non-limiting examples of opticalelements and substrates, as well as ophthalmic elements and substrates,that can be used in conjunction with various non-limiting embodiments ofoptical elements and ophthalmic elements disclosed herein are set forthabove in detail.

As discussed above, the time required to align thick, single-phaseliquid crystal coatings is generally longer than the time required toalign thinner coatings of the same material. Thus, although notrequired, according to certain non-limiting embodiments wherein opticalelements having thick alignment facilities are desired, the alignmentfacility can comprise a plurality of at least partial coatings. Forexample, with continued reference to FIG. 2, according to onenon-limiting embodiment, the at least one at least partial coating 224of alignment facility 223 can comprise a first at least partial coating226 comprising an at least partially ordered liquid crystal material andat least one additional at least partial coating 228 comprising an atleast partially aligned liquid crystal material on at least a portion ofthe first at least partial coating 226.

Although not limiting herein, for example, according to variousnon-limiting embodiments, the first at least partial coating 226 canhave a thickness (generally indicated 227) ranging from: 0.5 to 20microns, 0.5 to 10 microns, and 2 to 8 microns. Further, for example andwithout limitation, according to various non-limiting embodimentsdisclosed herein, the at least one additional at least partial coating228 can have a thickness (generally indicated 229) ranging from 1 micronto 25 microns, can further have a thickness ranging from 5 microns to 20microns. According to still another non-limiting embodiment, at leastone additional at least partial coating can have a thickness greaterthan 6 microns, and can further have a thickness of at least 10 microns.

Still further, according to various non-limiting embodiments disclosedherein, the first at least partial coating 226 can be thinner than theat least one additional at least partial coating 228. For example andwithout limitation, in one non-limiting embodiment, the first at leastpartial coating 226 can have a thickness ranging from 2 microns to 8microns and the at least one additional at least partial coating 228 canhave a thickness ranging from 10 microns to 20 microns. Non-limitingmethods of making such coatings are described above in detail.

Further according to various non-limiting embodiments disclosed herein,the at least partial coating(s) (or sheets) of the alignment facilitycan further comprise at least one additive chosen from alignmentpromoters, kinetic enhancing additives, photoinitiators, thermalinitiators, polymerization inhibitors, solvents, light stabilizers (suchas, but not limited to, ultraviolet light absorbers and lightstabilizers, such as hindered amine light stabilizers (HALS)), heatstabilizers, mold release agents, rheology control agents, levelingagents (such as, but not limited to, surfactants), free radicalscavengers, and adhesion promoters (such as hexanediol diacrylate andcoupling agents).

As used herein, the term “alignment promoter” means an additive that canfacilitate at least one of the rate and uniformity of the alignment of amaterial to which it is added. Non-limiting examples of alignmentpromoters that can be present in the at least partial coatings (andsheets) according to various non-limiting embodiments disclosed hereininclude those described in U.S. Pat. No. 6,338,808 and U.S. PatentPublication No. 2002/0039627, which are hereby specifically incorporatedby reference herein.

Non-limiting examples of kinetic enhancing additives that can be presentin the at least partial coatings (and sheets) according to variousnon-limiting embodiments disclosed herein include epoxy-containingcompounds, organic polyols, and/or plasticizers. More specific examplesof such kinetic enhancing additives are disclosed in U.S. Pat. No.6,433,043 and U.S. Patent Publication No. 2003/0045612, which are herebyincorporated by reference herein.

Non-limiting examples of photoinitiators that can be present in the atleast partial coatings (and sheets) according to various non-limitingembodiments disclosed herein include cleavage-type photoinitiators andabstraction-type photoinitiators. Non-limiting examples of cleavage-typephotoinitiators include acetophenones, α-aminoalkylphenones, benzoinethers, benzoyl oximes, acylphosphine oxides and bisacylphosphine oxidesor mixtures of such initiators. A commercial example of such aphotoinitiator is DAROCURE® 4265, which is available from CibaChemicals, Inc. Non-limiting examples of abstraction-typephotoinitiators include benzophenone, Michler's ketone, thioxanthone,anthraquinone, camphorquinone, fluorone, ketocoumarin or mixtures ofsuch initiators.

Another non-limiting example of a photoinitiator that can be present inthe at least partial coatings (and sheets) according to variousnon-limiting embodiments disclosed herein is a visible lightphotoinitiator. Non-limiting examples of suitable visible lightphotoinitiators are set forth at column 12, line 11 to column 13, line21 of U.S. Pat. No. 6,602,603, which is specifically incorporated byreference herein.

Non-limiting examples of thermal initiators include organic peroxycompounds and azobis(organonitrile) compounds. Specific non-limitingexamples of organic peroxy compounds that are useful as thermalinitiators include peroxymonocarbonate esters, such astertiarybutylperoxy isopropyl carbonate; peroxydicarbonate esters, suchas di(2-ethylhexyl) peroxydicarbonate, di(secondarybutyl)peroxydicarbonate and diisopropylperoxydicarbonate;diacyperoxides, such as 2,4-dichlorobenzoyl peroxide, isobutyrylperoxide, decanoyl peroxide, lauroyl peroxide, propionyl peroxide,acetyl peroxide, benzoyl peroxide and p-chlorobenzoyl peroxide;peroxyesters such as t-butylperoxy pivalate, t-butylperoxy octylate andt-butylperoxyisobutyrate; methylethylketone peroxide, andacetylcyclohexane sulfonyl peroxide. In one non-limiting embodiment thethermal initiators used are those that do not discolor the resultingpolymerizate.

Non-limiting examples of azobis(organonitrile) compounds that can beused as thermal initiators include azobis(isobutyronitrile),azobis(2,4-dimethylvaleronitrile) or a mixture thereof.

Non-limiting examples of polymerization inhibitors include:nitrobenzene, 1,3,5-trinitrobenzene, p-benzoquinone, chloranil, DPPH,FeCl₃, CuCl₂, oxygen, sulfur, aniline, phenol, p-dihydroxybenzene,1,2,3-trihydroxybenzene, and 2,4,6-trimethylphenol.

Non-limiting examples of solvents that can be present in the at leastpartial coating (and sheets) according to various non-limitingembodiments disclosed herein include those that will dissolve solidcomponents of the coating, that are compatible with the coating and theelements and substrates, and/or can ensure uniform coverage of theexterior surface(s) to which the coating is applied. Potential solventsinclude, but are not limited to, the following: acetone, amylpropionate, anisole, benzene, butyl acetate, cyclohexane, dialkyl ethersof ethylene glycol, e.g., diethylene glycol dimethyl ether and theirderivates (sold as CELLOSOLVE® industrial solvents), diethylene glycoldibenzoate, dimethyl sulfoxide, dimethyl formamide, dimethoxybenzene,ethyl acetate, isopropyl alcohol, methyl cyclohexanone, cyclopentanone,methyl ethyl ketone, methyl isobutyl ketone, methyl propionate,propylene carbonate, tetrahydrofuran, toluene, xylene, 2-methoxyethylether, 3-propylene glycol methyl ether, and mixtures thereof.

Further, as previously discussed, one or more optical dyes can be incontact with at least partial coatings (and sheets) of the alignmentfacilities according to various non-limiting embodiments disclosedherein.

Referring again to FIG. 2, in addition to the at least one at leastpartial coating 224 comprising the at least partially ordered liquidcrystal material, the ophthalmic element 220 can further comprise anorientation facility 230 interposed between at least a portion of the atleast one at least partial coating 224 of the alignment facility 223 andthe ophthalmic substrate 222. Non-limiting examples of suitableorientation facilities and methods of making the same are set forthabove.

Moreover, although not shown in the figures, in addition to thealignment facility, the optical elements according to variousnon-limiting embodiments disclosed herein can further comprise at leastone at least partial primer coating interposed between at least aportion of the at least partial coating of the alignment facility andthe optical substrate, or between at least a portion of an orientationfacility and the optical substrate. Non-limiting examples of suchcoatings are set forth above in detail.

Referring now to FIG. 3, another non-limiting embodiment provides anoptical element (generally indicated 330) comprising an opticalsubstrate 332, and an alignment facility (generally indicated 333) foran optical dye connected to at least a portion of the optical substrate.According to this non-limiting embodiment, the alignment facility 333comprises an at least partial coating 334 having a thickness (generallyindicated 335) greater than 6 microns and comprising an at leastpartially ordered liquid crystal material. Further, according to thisnon-limiting embodiment, the at least partial coating 334 can havethickness 335 of at least 10 microns. According to still othernon-limiting embodiments, at least partial coating 334 can have athickness 335 ranging from 50 microns to 1000 microns or more.Non-limiting methods and material for making such coatings are describedabove in detail.

Another non-limiting embodiment provides an alignment facility for anoptical dye comprising an at least partial coating comprising an atleast partially ordered phase-separated polymer, the phase-separatedpolymer comprising a matrix phase comprising a liquid crystal materialat least a portion of which is at least partially ordered in at least afirst general direction and a guest phase comprising a liquid crystalmaterial distributed within the matrix phase, wherein at least a portionof the liquid crystal material of the guest phase is at least partiallyordered in at least a second general direction that is generallyparallel to at least the first general direction. Further, according tothis non-limiting embodiment, alignment facility can be connected to anoptical substrate to form an optical element. For example, according toone non-limiting embodiment there is provided an optical elementcomprising an optical substrate and an alignment facility for an opticaldye connected to at least a portion of the optical substrate, thealignment facility comprising an at least partial coating comprising anat least partially ordered phase-separated polymer. Non-limiting methodsof forming such alignment facilities are described above.

Referring now to FIG. 4, another non-limiting embodiment provides analignment facility (generally indicated 443) for an optical dyecomprising a sheet 444 comprising an at least partially ordered liquidcrystal polymer 446 having at least a first general direction and an atleast partially ordered liquid crystal material 447 distributed withinat least a portion of the liquid crystal polymer 446, wherein the atleast partially ordered liquid crystal material 447 has at least asecond general direction that is generally parallel to at least thefirst general direction of the liquid crystal polymer 446. According toone non-limiting embodiment, the sheet 444 can be formed from aphase-separating polymer system as discussed above. Alternatively,according to another non-limiting embodiment, the sheet 444 can beformed using the imbibition techniques previously discussed.

Although not limiting herein, as discussed above, according to variousnon-limiting embodiments, the sheet can be connected to at least aportion of an optical substrate. Non-limiting methods of connecting thesheet to at least a portion of the optical substrate include:laminating, fusing, in-mold casting, adhesively bonding, andcombinations thereof. As used herein, the term “in-mold casting”includes a variety of casting techniques, such as but not limited to:overlaying, wherein the sheet is placed in a mold and the substrate isformed (for example by casting) over at least a portion of thesubstrate; and injection molding, wherein the substrate is formed aroundthe sheet.

One non-limiting embodiment provides an optical element comprising anoptical substrate and an alignment facility comprising a sheetcomprising an at least partially ordered liquid crystal polymer havingat least a first general direction and an at least partially orderedliquid crystal material having at least a second general directiondistributed within at least a portion of the at least partially orderedliquid crystal polymer matrix. Further, according to this non-limitingembodiment, at least the second general direction can be generallyparallel to at least the first general direction of the liquid crystalpolymer. As discussed above, a variety of methods can be used to connectthe sheet of the alignment facility to the optical substrate.

Another non-limiting embodiment provides an alignment facility for anoptical dye comprising an at least partial coating of interpenetratingpolymer network comprising a polymer and an at least partially orderedliquid crystal material. Further, as previously discussed, the alignmentfacility can be connected to at least a portion of an optical substrate.For example, one non-limiting embodiment provides an optical elementcomprising an optical substrate and an alignment facility for an opticaldye connected to at least a portion of the optical substrate, whereinthe alignment facility comprises an at least partial coating of aninterpenetrating polymer network comprising a polymer and an at leastpartially ordered liquid crystal material. Non-limiting methods offorming at least partial coatings comprising an at least partiallyaligned interpenetrating polymer network are set forth above.

Various non-limiting embodiments disclosed herein will now beillustrated in the following non-liming examples.

EXAMPLES Polymerization Induced Phase Separation Examples

Liquid Crystal Monomers (LCM) 1-3 describe the preparation of the liquidcrystal monomers used in the Examples. Photochromic/Dichroic (PC/DD)compound describes the preparation of PC/DD-1 used in the Examples.Photochromic Compound (PC) describes the preparation of PC-1 used in theExamples. Dichroic Dye (DD) describes DD-1 used in the Examples.Examples 1-7 and Comparative Example 1 (CE-1) describe the formulationscontaining the LCM prepared according to the method described with Table2. Example 8 describes the preparation and testing of the samples coatedwith Examples 1-7 and CE-1.

The following abbreviations were used for the chemicals listed:

-   Al(OiPr)₃—aluminum triisopropylate-   DHP—3,4-dihydro-2H-pyran-   DCC—dicyclohexylcarbodiimide-   DMAP—4-dimethylaminopyridine-   PPTS—pyridine p-toluenesulfonate-   pTSA—p-toluenesulfonic acid-   NMP—N-methylpyrrolidone-   BHT—butylated hydroxytoluene-   THF—tetrahyrdofuran-   mCPBA—3-chloroperoxybenzoic acid-   DMAc—N,N-dimethylacetamide    LCM-1    Step 1

To a reaction flask was added 4-hydroxybenzoic acid (90 grams (g), 0.65mole (mol)), ethyl ether (1000 milliliters (mL)) and pTSA (2 g). Theresulting suspension was stirred at room temperature. DHP (66 g, 0.8mol) was added to the mixture. The suspension turned clear soon afterthe addition of DHP and a white crystalline precipitate formed. Themixture was then stirred at room temperature overnight. The resultingprecipitates were collected by vacuum filtration and washed with ethylether. White crystals were recovered as the product (90 g, 62% yield).Nuclear Magnetic Resonance (NMR) showed that the product had a structureconsistent with 4-(tetrahydro-2H-pyran-2-yloxy)benzoic acid.

Step 2

To a reaction flask was added 4-(tetrahydro-2H-pyran-2-yloxy)benzoicacid (65.5 g, 0.295 mol) from Step 1, 4-(trans-4-pentylcyclohexyl)phenol(70.3 g, 0.268 mol), DCC (66.8 g, 0.324 mol), DMAP (3.3 g) and methylenechloride (1 L). The resulting mixture was mechanically stirred at 0° C.for 30 minutes, then at room temperature for 2 hours. The resultingsolids were filtered off. The solution was concentrated until whitecrystals started to precipitate. One liter of methanol was added intothe mixture with stirring. The precipitated solid crystalline productwas collected by vacuum filtration and washed with methanol. Whitecrystals (126 g) were recovered as the product. NMR showed that theproduct had a structure consistent with4-(trans-4-pentylcyclohexyl)phenyl4-(tetrahydro-2H-pyran-2-yloxy)benzoate.

Step 3

The product from Step 2,4-(trans-4-pentylcyclohexyl)phenyl 4-(tetrahydro-2H-pyran-2-yloxy)benzoate (120 g, 0.26 mol), was dissolved in1,2-dichloroethane (600 mL) in a reaction flask. Methanol (300 mL) andPPTS (9 g, 36 millimole (mmol)) was added. The mixture was heated toreflux and maintained at reflux for 6 hours. Upon standing at roomtemperature overnight, white crystals precipitated out which werecollected by vacuum filtration. The mother liquid was concentrated andmore white crystals precipitated out with the addition of methanol. Thecombined white crystalline product (90 g) was washed with methanol(about 300 mL) three times and air dried. NMR showed that the producthad a structure consistent with 4-(trans-4-pentylcyclohexyl)phenyl4-hydroxybenzoate.

Step 4

To a reaction flask was added the product of Step3,4-(trans-4-pentylcyclohexyl) phenyl 4-hydroxybenzoate (70 g, 190mmol), 6-chloro-1-hexanol (30 g, 220 mmol), NMP (300 mL), sodium iodide(6 g), and potassium carbonate (57 g, 410 mmol). The resulting mixturewas vigorously stirred at 85-90° C. for 4 hours. The resulting mixturewas extracted using 1/1 volume ratio of ethyl acetate/hexanes (1 L) andwater (500 mL). The separated organic layer was washed several timeswith water to remove NMP and then dried over anhydrous magnesium sulfate(MgSO₄). After concentration, acetonitrile was added to precipitate theproduct. White crystals (76 g) were collected by vacuum filtration. NMRshowed that the product had a structure consistent with4-(trans-4-pentylcyclohexyl)phenyl 4-(6-hydroxyhexyloxy)benzoate.

Step 5

To a reaction flask was added the product of Step 4,4-(trans-4-pentylcyclohexyl) phenyl 4-(6-hydroxyhexyloxy)benzoate (2 g,4.3 mmol), epsilon -caprolactone (2.94 g, 26 mmol), Al(OiPr)₃ (0.26 g,1.3 mmol) and methylene chloride (40 mL). The resulting mixture wasstirred at room temperature for 8 hours. BHT (9 milligram (mg), 0.04mmol), DMAP (0.05 g, 0.43 mmol) and N,N-diethylaniline (1.8 g, 15 mmol)was added to the mixture and the mixture was stirred for half an hour.Freshly distilled methacryloyl chloride (1.34 g, 13 mmol) was then addedto the mixture. After stirring at room temperature for 8 hours, themixture was washed with 5 weight percent NaOH aqueous solution threetimes, with an aqueous 1 Normal (N)HCl solution three times and thenwith the 5 weight percent NaOH aqueous solution one more time. Note thatwhenever weight percent is reported herein, it is based on the totalweight of the solution. The organic layer was separated and dried overanhydrous MgSO₄. After concentration, a methanol washing was done byadding 100 mL of methanol to the recovered oil with stirring. After 10minutes, the resulting cloudy mixture was left at room temperature.After the cloudiness of the mixture cleared, methanol on top of themixture was decanted. This methanol wash was done three times. Therecovered oil was re-dissolved in ethyl acetate, dried over anhydrousMgSO₄ and concentrated. A viscous liquid (3.9 g) was recovered as theproduct. NMR showed that the product had a structure consistent with1-(6-(6-(6-(6-(6-(6-(6-(6-(6-(4-(4-(trans-4-pentylcyclohexyl)phenoxycarbonyl)phenoxy)hexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-6-oxohexyloxy)-2-methylprop-2-en-1-one with n having an averagedistribution of 8.1 as represented by the following graphic formula.

Step 1

A suspension of methyl 4-hydroxy benzoate (0.800 kilograms (Kg), 5.26mol), 8-chloro-1-octanol (0.950 Kg, 5.76 mol), sodium iodide hydrate(97.6 g, 0.528 mol) and sodium carbonate anhydrous (1.670 Kg, 15.78 mol)in 4,000 mL of DMAc in a reaction flask was stirred and heated to about110° C. for 10 hours. The solution was cooled to room temperature andfiltered. The solid was washed with 1,400 mL of DMAc. The filtrate wasconcentrated under reduced pressure and the resulting residue was pouredinto 40 liters of water under stirring. White solid was obtained afterfiltration and it was washed with water. The product was used for nextstep without further purification.

Step 2

The crude product from Step 1 was mixed with sodium hydroxide (0.504 Kg,12.62 mol) and 5,000 mL of ethanol and heated to reflux for 4 hours. Thesolution was cooled to room temperature and acidified with 6 L of 3 NHCl solution to a pH of 6-7. A large amount of white solid was formed.The solid was filtered and washed by water and dried to give 1.20 Kg ofthe final product. The two step yield was approximately 84.8%. NMRshowed that the product had a structure consistent with4-(8-hydroxyoctyloxy)benzoic acid.

Step 3

A suspension of 4-(8-hydroxyoctyloxy)benzoic acid from Step 2 (133.17 g,0.500 mol) and pTSA (0.95 g, 0.005 mol) in a reaction flask containing550 mL of THF was stirred at room temperature, and DHP (55 mL, 0.600mol) was added over 1 hour. The reaction mixture was then heated to 50°C. After stirring for 24 hours at this temperature, DHP (37 mL, 0.400mol) was added over 1 hour and the reaction mixture was stirred for 24hours. The solution was cooled to room temperature and filtered throughCelite, and the filtrate was concentrated. The crude product wasdissolved in 100 mL of CH₂Cl₂ and filtered through Celite, and thefiltrate was concentrated and poured into 1,000 mL of petroleum ether.The precipitates was collected by filtration and dried in vacuum to givethe final product. The yield was 110.0 g (62.7%). NMR showed that theproduct had a structure consistent with4-(8-(tetrahydro-2H-pyran-2-yloxy)octyloxy)benzoic acid.

Step 4

To a flask charged with nitrogen gas, was added p-hydroquinone (500 g,4.53 mol), sodium carbonate (250 g, 2.35 mol) and water (7.5 L) and themixture stirred at room temperature. After a solution formed, benzylchloroformate (875 g, 5.13 mol) was added dropwise within 4 hours. Thereaction mixture was then stirred overnight and during that time asuspension formed. The precipitates were separated out by filtration,washed with water, purified by recrystallization in ethanol/water (75:25on a volume basis) and dried in vacuum to give the final product. Theyield was 452 g (40.9%). NMR showed that the product had a structureconsistent with benzyl 4-hydroxyphenyl carbonate.

Step 5

To a solution of benzyl 4-hydroxyphenyl carbonate from Step 4 (37.27 g,0.15 mol), 4-(8-(tetrahydro-2H-pyran-2-yloxy)octyloxy)benzoic acid fromStep 3 (52.60 g, 0.15 mol) and DMAP (a catalytic amount) in a reactionflask containing dichloromethane (300 mL), was added DCC (37.13 g, 0.18mol) in portions at room temperature. After stirring overnight, theprecipitates were removed by filtration. The filtrate was concentratedto give an oil-like product, which was then crystallized in ethyl etherand suspended in methanol with stirring for 6 hours, and afterfiltration the yield was 61.4 g (71.0%). NMR showed that the product hada structure consistent with 4-(benzyloxycarbonyloxy)phenyl4-(8-(tetrahydro-2H-pyran -2-yloxy)octyloxy)benzoate.

Step 6

To a reaction flask containing a solution of4-(benzyloxycarbonyloxy)phenyl4-(8-(tetrahydro-2H-pyran-2-yloxy)octyloxy)benzoate from Step 5 (306.0g, 0.53 mol) in 3 L of THF was added 15.3 g of a 50 weight percentaqueous suspension of palladium, 10 weight percent on activated carbonand the flask charged with hydrogen at ambient atmosphere. Afterstirring 2 days, the suspension was filtered through Celite. Thefiltrate was then concentrated to dryness. The crude oil-like productformed crystals in ethyl ether to give the final product. The yield was208.5 g (88.9%). NMR showed that the product had a structure consistentwith 4-hydroxyphenyl4-(8-(tetrahydro-2H-pyran-2-yloxy)-octyloxy)benzoate.

Step 7

A mixture of 4-pentylbenzoic acid (10.0 g, 52.0 mmol), 4-hydroxyphenyl4-(8-(tetrahydro-2H-pyran-2-yloxy)-octyloxy)benzoate from Step 6 (23.0g, 52.0 mmol), DCC (11.8 g, 57.2 mmol), and DMAP (1.3 g, 10.4 mmol) in400 mL of CH₂Cl₂ in a 500 mL single-necked, round-bottomed flask wasstirred at room temperature under nitrogen atmosphere overnight. Thewhite precipitate that formed during the reaction was removed byfiltration through a Buchner funnel. The filtrate was concentrated andfiltered again. The removal of the solvent yielded a white product.Precipitation from methylene chloride/methanol (1/10 on a volume basis)provided the final product, which was used for the next step withoutfurther purification. The yield was 29.0 g (90.3%). NMR showed that theproduct had a structure consistent with4-(4-(8-hydroxyoctyloxy)benzoyloxy)phenyl-4-pentylbenzoate.

Step 8

To a solution of epsilon-caprolactone (2.14 g, 18.8 mmol) and theproduct from Step 7,4-(4-(8-hydroxyoctyloxy)benzoyloxy)phenyl4-pentylbenzoate (5.0 g, 9.4 mmol) in 100 mL of CH₂Cl₂ in a 250 mL ofsingle-necked, round bottomed flask was added AI(OiPr)₃ (0.58 g, 2.8mmol). The reaction was stirred for 12 hours at room temperature undernitrogen atmosphere. The resulting solution was washed with 1 N HCl (100mL, three times), 5 weight percent of NaOH aqueous solution (100 mL,once), and saturated brine (100 mL, three times). The resulting mixturewas dried over anhydrous MgSO₄, flashed through a silica gel plugcolumn, and the removal of the solvent yielded 7.0 g of a waxy solid(98%) as the product. NMR showed that the product had a structureconsistent with1-(6-(6-(4-(4-(4-pentylbenzoyloxy)phenyloxycarbonyl)phenoxy)octyloxy)-6-oxohexyloxy)-6-oxohexanolwith n having an average distribution of 2 as represented by thefollowing graphic formula.

Step 1

To a solution of methyl 4-hydroxybenzoate (38.0 g, 0.25 mol),hex-5-en-1-ol (26.0 g, 0.255 mol), and triphenylphosphine (72.0 g, 0.275mol) in a reaction flask containing 200 mL of THF was added diisopropyldiazodicarboxylate (56.0 g, 0.275 mol) dropwise. The resulting mixturewas stirred at room temperature overnight. After the removal of thesolvent, the crude product was purified by column chromatography onsilica gel by eluting with ethyl acetate/hexane (9:1 on a volume basis)to provide a yellow liquid as the final product, which was used for thenext step without further characterization.

Step 2

A mixture of the product of Step 1 and potassium hydroxide (28.0 g, 0.50mol) in a reaction flask containing 200 mL of water/ethanol (1:1 on avolume basis) was heated to reflux for two hours. The ethanol wasremoved by evaporation and the concentrated solution was acidified withconcentrated HCl to pH 5-6. A large amount of white precipitate formedand was collected by filtration. After washing with deionized water anddrying under vacuum, a white solid was obtained. The yield was 55 g(99.6%). NMR showed that the product had a structure consistent with4-(hex-5-enyloxy)benzoic acid.

Step 3

The mixture of 4-(hex-5-enyloxy)benzoic acid from Step 2 (6.6 g, 0.03mol), 4-pentylphenol (4.9 g, 0.03 mol), DCC (6.2 g, 0.03 mol), and DMAP(0.4 g, 0.003 mol) in a reaction flask containing 50 mL of methylenechloride was stirred at room temperature overnight. After the removal ofthe solvent, the crude product was purified by column chromatography onsilica gel by eluting with ethyl acetate/hexane (1:9 on a volume basis)to provide a colorless crystalline product. The yield was 7.35 g(66.8%). NMR showed that the product had a structure consistent with4-pentylphenyl 4-(hex-5-enyloxy)benzoate.

Step 4

A solution of 4-pentylphenyl 4-(hex-5-enyloxy)benzoate from Step 3 (7.35g, 0.02 mol) and mCPBA (6.0 g, 0.025 mol) in a reaction flask containing50 mL of methylene chloride was stirred at room temperature overnight. Alarge amount of precipitate formed and was removed by filtration. Theresulting filtrate was washed with a 5 weight percent sodium bicarbonatesolution and water and dried over anhydrous MgSO₄. The removal of thesolvent yielded a crude product, which was purified by columnchromatography on silica gel by eluting with ethyl acetate/hexane (1:9to 2:8 on a volume basis) to provide a colorless crystalline product.The yield was 6.5 g (85.5%). NMR showed that the product had a structureconsistent with 4-pentylphenyl 4-(4-(oxiran-2-yl)butoxy)benzoate.

Photochromic/Dichroic Compound (PC/DD)

PC/DD-1 was prepared following the procedures of U.S. Pat. No.7,342,112, which disclosure is incorporated herein by reference. NMRanalysis showed the product to have a structure consistent with thefollowing name:

-   -   PC/DD-1—3-(4-fluorophenyl-3-(4-piperazinophenyl)-13-ethyl-13-methoxy-6-methoxy-7-(4-(4-(4-(trans)phentylcyclohexyl)benzoyloxy)        -phenyl)benzoyloxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.        Photochromic Compound (PC)

PC-1 was prepared following the procedures of U.S. Pat. Nos. 5,645,767and 6,296,785 B1, which disclosures are incorporated herein byreference. NMR analysis showed the product to have a structureconsistent with the following name:

-   -   PC-1—3-(4-methoxyphenyl)-3-(4-morpholinophenyl)-13,13-dimethyl-3H,13H-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.        Dichroic Dye (DD)

DD-1 was prepared according to the following procedure. A mixture of4-[-(phenylazo)-1-naphthylazo]phenol (Disperse Orange 13, commerciallyavailable from Aldrich, Milwaukee, Wis.) (14.0 g, 0.04 mol), ethyl4-(bromomethyl)benzoate (11.7 g, 0.048 mol), potassium carbonate (22.2g, 0.16 mol), and potassium iodide (0.7 g, 0.004 mol) in a reactionflask containing 150 mL of 2-butanone was stirred and heated to refluxfor 5 hours. The reaction was allowed to cool down to room temperatureand filtered. The remaining solid was washed with de-ionized water threetimes and dried in air. Recrystallization from ethyl acetate providedthe final product. The yield was 12.8 g (62%). NMR analysis showed theproduct to have a structure consistent with the following name:

-   -   DD-1—Ethyl        4-((4-((E)-(4-((E)-phenyldiazenyl)naphthalen-1-yl)diazenyl)phenoxy)methyl)benzoate.

Examples 1-7

Examples 1-7 were prepared according to the formulation listed in Table1 using the specific LCM, DD, PC/DD and PC listed in Table 2.Comparative Example (CE) 1 was prepared following the same procedureexcept that the weight percent of the Host LCM was 60 instead of 50percent and there was no Guest LCM.

TABLE 1 Weight Percent (based on the total weight of the solution of theLCMs and the Materials solvent unless specified otherwise) Host LCMs 50Guest LCMs 10 Solvent⁽¹⁾ 40 Initiator⁽²⁾ 1.5 based on LCM solidsStabilizer⁽³⁾ 0.1 based on LCM solids Dye when present (PC/DD, PC, or6.0 based on LCM solids combination of PC/DD & DD) ⁽¹⁾Solvent was 99weight percent anisole and 1 weight percent surfactant sold as BYK ®-346additive by BYK Chemie, USA. ⁽²⁾Initiator was IRGACURE ® 819, aphotoinitiator that is available from Ciba-Geigy Corporation.⁽³⁾Stabilizer was 2-methyl hydroquinone.

TABLE 2 Guest Example # Host LCMs LCMs Dye 1RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ ZLI-1565 PC/DD-1 RM-82⁽⁷⁾ (1:1:1:1) 2RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ ZLI-1565 PC-1 RM-82⁽⁷⁾ (1:1:1:1) 3RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ ZLI-1565 DD-1 & RM-82⁽⁷⁾ (1:1:1:1) PC/DD-1(1:1) 4 RM-257⁽⁴⁾/LCM-1 ZLI-1565 PC/DD-1 (1:1) 5RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ LCM-2 PC/DD-1 RM-82⁽⁷⁾ (1:1:1:1) 6RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ LCM-3 PC/DD-1 RM-82⁽⁷⁾ (1:1:1:1) 7RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ ZLI-1565 PC/DD-1 RM-82⁽⁷⁾ (1:1:1:1) CE-1RM-257⁽⁴⁾/RM-105⁽⁵⁾/RM-23⁽⁶⁾/ — PC/DD-1 RM-82⁽⁷⁾ (1:1:1:1) ⁽⁴⁾RM 257 isa liquid crystal monomers available from EMD Chemicals, Inc. and isreported to have the molecular formula of C₃₃H₃₂O₁₀. ⁽⁵⁾RM 105 is aliquid crystal monomers available from EMD Chemicals, Inc. and isreported to have the molecular formula of C₂₃H₂₆O₆. ⁽⁶⁾RM 23 is a liquidcrystal monomers available from EMD Chemicals, Inc. and is reported tohave the molecular formula of C₂₉H₂₃NO₅. ⁽⁷⁾RM 82 is a liquid crystalmonomers available from EMD Chemicals, Inc. and is reported to have themolecular formula of C₂₃H₂₆O₆. ⁽⁸⁾ZLI-1565 is a liquid crystalformulation available from Merck.

To a vial (20 mL) containing a magnetic stir bar was added each of theliquid crystal monomers, dyes, stabilizer, and initiator. Solvent wasadded to the contents in the vial, and the vial was capped and wrappedwith aluminum foil and then positioned on a magnetic stirrer. Theresulting mixture was heated to 80° C. and stirred for about 30 minuntil the solution became clear. The solution was cooled to roomtemperature and a small drop of solution was taken by a capillary forphase transition study. Afterwards, the resulting solution was cooled toroom temperature and stored in darkness.

Example 8 Preparation of Samples Coated with Examples 1-7 and CE-1

Each of the Examples and CE was used in the procedure describedhereinafter in Parts A-E, to prepare at least partial coatings on thesurface of a substrate. Prior to preparation, the phase transitions ofeach example were determined by the procedure described in Part F. TheAbsorption Ratios and optical response measurements are described inPart G.

Part A—Substrate Cleaning

Square substrates measuring 5.08 cm by 5.08 cm by 0.318 cm (2 inches by2 inches by 0.125 inch) prepared from CR-39® monomer were obtained fromHomalite, Inc., Wilmington, Del. Each substrate was cleaned by wipingwith a tissue soaked with acetone and drying with a stream of nitrogengas.

Part B—Alignment Layer Application

A solution of a photo-orientable polymer network available as Staralign®2200 CP10 solution from Huntsman Advanced Materials, Basel, Switzerland,was diluted to 4 weight percent in cyclopentanone. The resultingsolution was applied by spin-coating to a portion of the surface of thetest substrate by dispensing approximately 1.0 mL of the Staralign®solution and spinning the substrates at 1000 revolutions per minute(rpm) for 10 seconds. Afterwards, the coated substrates were placed inan oven maintained at 135° C. for 30 minutes.

For the alignment layer produced by rubbing, triacetate cellulose (TAC)was dissolved in cyclopentanone at 4 weight percent and applied byspin-coating to a portion of the surface of the test substrate bydispensing approximately 1.0 mL of the TAC solution and spinning thesubstrates at 500 rpm for 3 seconds followed by 1000 rpm for 10 seconds.Afterwards, the coated substrates were placed in an oven maintained at140° C. for 60 minutes.

Part C—Orientation of the Alignment Layer

After application, the photo-orientable polymer network was at leastpartially ordered by exposure to linearly polarized ultravioletradiation for 5 minute at a peak intensity of 80-100 Watts/m² of UVA(320-390 nm) as measured using International Light Research Radiometer,Model IL-1700 with a detector system comprising a Model SED033 detector,B Filter and diffuser. The output display of the radiometer wascorrected (factor values set) against a Licor 1800-02 OpticalCalibration Calibrator in order to display values representing Watts persquare meter UVA. The source of linearly polarized UV radiation was amercury arc lamp (Model 69910) from Newport Oriel equipped with anintensity controller Model 68951. The light source was oriented suchthat the radiation was linearly polarized in a plane perpendicular tothe surface of the substrate. After ordering at least a portion of thephoto-orientable polymer network, the substrates were cooled to roomtemperature and kept covered.

The substrates having the TAC layer were oriented by rubbing the coatedsurface with velvet uni-directionally 20 times.

Part D—Application of the Examples and Comparative Examples

Prior to application, 10 weight percent of MgSO₄ was added to each ofthe Examples and the Comparative Example and the resulting mixture wasstirred for an hour at room temperature and subject to centrifugefiltration using a Millipore Ultrafree-MC (Durapore PVDF 5 um)filtration device in a Sovall Legend Micro 21 centrifuge at 10,000 rpmfor 5 min. A small drop of filtrate was taken by a capillary for phasetransition study. Material not used for the subsequent coating step wasstored in darkness.

The Examples and Comparative Example were applied by spin-coating to thealigned layer on the substrates by spin-coating to a portion of thesurface of the test substrate by dispensing 400 μL of the solution andspinning the substrates at 400 rpm for 9 seconds followed by 800 rpm for15 seconds. Afterwards, the coated substrates were placed in aconvection oven maintained at 50° C. to 100° C. lower than thecorresponding clearing temperature (the temperature at which the liquidcrystals transform into the isotropic state, as indicated in Table 3)for 10 to 15 minutes followed by curing under an ultraviolet lamp in theIrradiation Chamber BS-03 from Dr. Gröbel UV-Elektronik GmbH, Ettlingen,Germany, in a nitrogen atmosphere for 30 minutes.

Part E—Application of Acrylate-Based Film

An acrylate-based film prepared according to the disclosure in U.S. Pat.No. 7,410,691, which disclosure is incorporated herein by reference, wasapplied by spin-coating onto the cured Example and Comparative Examplecoatings by dispensing approximately 1 mL of the acrylate-based coatingsolution and spinning the substrates at 2000 rpm for 10 seconds.Afterwards, the coated substrate was cured under an ultraviolet lamp inthe Irradiation Chamber BS-03 from Dr. Gröbel UV-Elektronik GmbH in anitrogen atmosphere for 15 minutes.

Part F—Measurement of Liquid Crystal Phase Transition Temperatures

Phase transition temperatures were determined by using a Leica DM 2500 Mpolarized optical microscope equipped with a Linkam LTS120 hot stage anda Linkam PE 94 temperature controller. A small drop of solution from acapillary pipet was placed on a microscope glass slide, and a stream ofnitrogen was used to evaporate the solvent. The glass slide was mountedon the sample stage so that the liquid crystal residue spot was in theoptical path of the microscope. Phase transition temperatures weremeasured by observing the samples during heating at a rate of 10° C./minstarting at 25° C. Phase below 25° C. was not determined. The sample washeated until it reached the isotropic phase and then cooled at 10°C./min to 25° C. to determine the phase transition temperatures duringthe cooling process as indicated in Table 3. The phases of the liquidcrystals were determined according to the texture that appeared duringthe heating and cooling processes. Textures of Liquid Crystals byDietrich Demus and Lothar Richter, published by Verlag Chemie, Weinheim& New York in 1978 was used in the identification of the differentliquid crystal phases listed in Table 3. This text, in its entirety, isincorporated herein by reference.

The following abbreviations were used in Table 3: N represents theNematic phase; I represents the Isotropic phase. Note that all numbersrepresent the temperature in ° C. at which the adjacent phaseabbreviation occurred. Each phase measured is separated by // meaningthat the phase extended until the next temperature or temperature rangelisted. For example, 25 N // 37 I, indicates that the Nematic phase waspresent from 25° C. to about 37° C. when the Isotropic phase occurred.Observation of the sample's phase started at room temperature (25° C.)and reported the next phase transition temperature.

TABLE 3 Example # Phase Transition temperature 1 25 N//78 I//73 N 2 25N//67 I//64 N 3 25 N//90 I//81 N 4 25 N//49 I//42 N 5 25 N//81 I//70 N 625 N//69 I//64 N 7 25 N//78 I//73 N CE-1 25 N//82 I//74 NPart G—Absorption Ratio and Optical Response Measurements

Absorption ratios for each coated substrates with dichroic dyes (DD)were determined as follows. A CARY 6000i UV-Visible spectrophotometerwas equipped with a self-centering sample holder mounted on a rotationstage (Model M-060-PD from Polytech, PI) and the appropriate software. Apolarizer analyzer (Moxtek ProFlux™ polarizer) was placed in the samplebeam before the sample. The instrument was set with the followingparameters: Scan speed=600 nm/min; Data interval=1.0 nm; Integrationtime=100 ms; Absorbance range=0−6.5; Y mode=absorbance;X-mode=nanometers and the scanning range was 380 to 800 nm. Options wereset for 3.5 SBW (slit band width), and double for beam mode. Baselineoptions were set for Zero/baseline correction. Also, 1.1 and 1.5 (˜2.6together) Screen Neutral Density filters were in the reference path forall scans. The coated substrate samples were tested in air, at roomtemperature (22.8° C.±2.8° C. (73° F.±5° F.)) maintained by the lab airconditioning system.

Orientation of the sample polarizer to be parallel and perpendicular tothe analyzer polarizer was accomplished in the following manner. TheCary 6000i was set to 443 nm for samples containing DD-1 and theabsorbance was monitored as the sample was rotated in small increments(0.1 to 5 degrees, e.g., 5,1, 0.5 and 0.1 degrees). The rotation of thesample was continued until the absorbance was maximized. This positionwas defined as the perpendicular or 90 degree position. The parallelposition was obtained by rotating the stage 90 degrees clockwise orcounter-clockwise. Alignment of the samples was achieved to ±0.1°.

The absorption spectra were collected at both 90 and 0 degrees for eachsample. Data analysis was handled with the Igor Pro software availablefrom WaveMetrics. The spectra were loaded into Igor Pro and theabsorbances were used to calculate absorption ratios at 443 nm. Thecalculated absorption ratios are listed in Table 4.

The λ_(max-vis) in the visible light range is the wavelength in thevisible spectrum at which the maximum absorption of the activated formof the photochromic compound or dichroic dye occurs. The λ_(max-vis) wasdetermined by testing the coated substrate in a CARY 6000i UV-Visiblespectrophotometer.

Prior to response testing on an optical bench, the substrates havingphotochromic compounds in the coatings were conditioned by exposing themto 365 nm ultraviolet light for 10 minutes at a distance of about 14 cmfrom the source in order to pre-activate the photochromic molecules. TheUVA irradiance at the sample was measured with a Licor Model Li-1800spectroradiometer and found to be 22.2 Watts per square meter. Thesamples were then placed under a halogen lamp (500 W, 120V) for about 10minutes at a distance of about 36 cm from the lamp in order to bleach,or inactivate, the photochromic compound in the samples. The illuminanceat the sample was measured with the Licor spectroradiometer and found tobe 21.9 Klux. The samples were then kept in a dark environment for atleast 1 hour prior to testing in order to cool and continue to fade backto a ground state.

An optical bench was used to measure the optical properties of thecoated substrates and derive the absorption ratio and photochromicproperties. Each test sample was placed on the optical bench with anactivating light source (a Newport/Oriel Model 66485 300-Watt Xenon arclamp fitted with a Uniblitz VS-25 high-speed computer controlled shutterthat momentarily closed during data collection so that stray light wouldnot interfere with the data collection process, a Schott 3 mm KG-1band-pass filter, which removed short wavelength radiation, neutraldensity filter(s) for intensity attenuation and a condensing lens forbeam collimation) positioned at a 30° to 35° angle of incidence to thesurface of the test sample. The arc lamp was equipped with a lightintensity controller (Newport/Oriel model 68950).

A broadband light source for monitoring response measurements waspositioned in a perpendicular manner to a surface of the test sample.Increased signal of shorter visible wavelengths was obtained bycollecting and combining separately filtered light from a 100-Watttungsten halogen lamp (controlled by a Lambda UP60-14 constant voltagepowder supply) with a split-end, bifurcated fiber optical cable. Lightfrom one side of the tungsten halogen lamp was filtered with a SchottKG1 filter to absorb heat and a Hoya B-440 filter to allow passage ofthe shorter wavelengths. The other side of the light was either filteredwith a Schott KG1 filter or unfiltered. The light was collected byfocusing light from each side of the lamp onto a separate end of thesplit-end, bifurcated fiber optic cable, and subsequently combined intoone light source emerging from the single end of the cable. A 4″ lightpipe was attached to the single end of the cable to insure propermixing. The broad band light source was fitted with a Uniblitz VS-25high-speed computer controlled shutter that momentarily opened duringdata collection.

Polarization of the light source was achieved by passing the light fromthe single end of the cable through a Moxtek, Proflux Polarizer held ina computer driven, motorized rotation stage (Model M-061-PD fromPolytech, PI). The monitoring beam was set so that the one polarizationplane (0°) was perpendicular to the plane of the optical bench table andthe second polarization plane (90°) was parallel to the plane of theoptical bench table. The samples were run in air, at 23° C.±0.1° C.(73.4° F.±0.2° F.) maintained by a temperature controlled air cell.

To align each sample, a second polarizer was added to the optical path.The second polarizer was set to 90° of the first polarizer. The samplewas placed in an air cell in a self-centering holder mounted on arotation stage (Model No M-061. PD from Polytech, PI). A laser beam(Coherent-ULN 635 diode laser) was directed through the crossedpolarizers and sample. The sample was rotated (in 3° steps as coursemoves and in 0.1° steps as fine moves) to find the minimum transmission.At this point the sample was aligned either parallel or perpendicular tothe Moxtek polarizer and the second polarizer as well as the diode laserbeam was removed from the optical path. The sample was aligned ±0.2°prior to any activation.

To conduct the measurements, each test sample containing a photochromicdye was exposed to 6.7 W/m² of UVA from the activating light source for10 to 20 minutes to activate the photochromic compound. An InternationalLight Research Radiometer (Model IL-1700) with a detector system (ModelSED033 detector, B Filter, and diffuser) was used to verify exposure atthe beginning of each day. Light from the monitoring source that waspolarized to the 0° polarization plane was then passed through thecoated sample and focused into a 1″ integrating sphere, which wasconnected to an Ocean Optics S2000 spectrophotometer using a singlefunction fiber optic cable. The spectral information, after passingthrough the sample, was collected using Ocean Optics OOIBase32 andOOIColor software, and PPG propriety software. While the photochromicmaterial was activated, the position of the polarizing sheet was rotatedback and forth to polarize the light from the monitoring light source tothe 90° polarization plane and back. Data was collected forapproximately 600 to 1200 seconds at 5-second intervals duringactivation. For each test, rotation of the polarizers was adjusted tocollect data in the following sequence of polarization planes: 0°, 90°,90°, 0°, etc.

Absorption spectra were obtained and analyzed for each test sample usingthe Igor Pro software (available from WaveMetrics). The change in theabsorbance in each polarization direction for each test sample wascalculated by subtracting out the 0 time (i.e., unactivated) absorptionmeasurement for the samples at each wavelength tested. Averageabsorbance values were obtained in the region of the activation profilewhere the photochromic response of the photochromic compound wassaturated or nearly saturated (i.e., the regions where the measuredabsorbance did not increase or did not increase significantly over time)for each sample by averaging absorbance at each time interval in thisregion. The average absorbance values in a predetermined range ofwavelengths corresponding λ_(max-vis)+/−5 nm were extracted for the 0°and 90° polarizations, and the absorption ratio for each wavelength inthis range was calculated by dividing the larger average absorbance bythe small average absorbance. For each wavelength extracted, 5 to 100data points were averaged. The average absorption ratio for thephotochromic compound was calculated by averaging these individualabsorption ratios.

Change in optical density (ΔOD) from the bleached state to the darkenedstate was determined by establishing the initial transmittance, openingthe shutter from the Xenon lamp to provide ultraviolet radiation tochange the test lens from the bleached state to an activated (i.e.,darkened) state. Data was collected at selected intervals of time,measuring the transmittance in the activated state, and calculating thechange in optical density according to the formula: ΔOD=log(% Tb/% Ta),where % Tb is the percent transmittance in the bleached state, % Ta isthe percent transmittance in the activated state and the logarithm is tothe base 10.

The fade half life (T ½) is the time interval in seconds for the ΔOD ofthe activated form of the photochromic compound in the test samples toreach one half the ΔOD measured after fifteen minutes, or aftersaturation or near-saturation was achieved, at room temperature afterremoval of the source of activating light, e.g., by closing the shutter.The results of these tests are presented in Table 4 below. Examinationof the results in Table 4 shows that Examples 1-7 demonstrated a lowerfade half life than Comparative Example 1.

TABLE 4 λ_(max-vis) Absorption T½ Example # (nm) Ratio (seconds) 1 6162.97 518 2 589 1.35 165 3 616 5.73 184 4 610 1.89 60 5 614 5.55 153 6611 4.89 620  7* 613 4.03 517 CE-1 620 4.27 >1800 *Example # denotes asample having an alignment layer of rubbed TAC.

It is to be understood that the present description and examplesillustrates aspects of the invention relevant to a clear understandingof the invention. Certain aspects of the invention that would beapparent to those of ordinary skill in the art and that, therefore,would not facilitate a better understanding of the invention have notbeen presented in order to simplify the present description. Althoughthe present invention has been described in connection with certainembodiments, the present invention is not limited to the particularembodiments or examples disclosed, but is intended to covermodifications that are within the spirit and scope of the invention, asdefined by the appended claims.

1. A phase-separating polymer system comprising: an at least partiallycured matrix phase comprising: a polymeric residue of at least a firstliquid crystal monomer; and a guest phase comprising: at least onephotoactive material selected from photochromic compounds andphotochromic-dichroic compounds; and at least one liquid crystalmaterial, wherein at least a portion of the guest phase separates fromat least a portion of the matrix phase during at least partial curing ofthe polymeric residue of the at least first liquid crystal monomer,wherein the at least one liquid crystal material of the guest phasecomprises a residue of at least one second liquid crystal monomer, suchthat the guest phase is an at least partially cured quest phase.
 2. Thephase-separating polymer system of claim 1, wherein at least one of thefirst liquid crystal monomer of the matrix phase and the at least oneliquid crystal material of the guest phase comprises at least onemesogen containing compound having a structure represented by Formula I:

where, a) each X is independently: i) a group R, ii) a group representedby-(L)_(y)-R, iii) a group represented by-(L)-R, iv) a group representedby-(L)_(w)-Q; v) a group represented by

vi) a group represented by-(L)_(y)-P; or vii) a group representedby-(L)_(w)-[(L)_(w)-P]_(y); b) each P is a reactive group independentlyselected from a group Q, hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈alkyl, C₁-C₁₈ alkoxy, amino(C₁-C₁₈)alkylene, C₁-C₁₈ alkylamino,di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl ether,(C₁-C₁₈)alkyl(C_(l)-C₁₈)alkoxy(C₁-C₁₈)alkylene, polyethyleneoxy,polypropyleneoxy, ethylene, acryloyl, acryloyloxy(C₁-C₁₈)alkylene,methacryloyl, methacryloyloxy(C₁-C₁₈)alkylene, 2-chloroacryloyl,2-phenylacryloyl, acryloylphenylene, 2-chloroacryloylamino,2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl ester,a styrene derivative, main-chain and side-chain liquid crystal polymers,siloxane derivatives, ethyleneimine derivatives, maleic acidderivatives, fumaric acid derivatives, unsubstituted cinnamic acidderivatives, cinnamic acid derivatives that are substituted with atleast one of methyl, methoxy, cyano and halogen, or substituted orunsubstituted chiral or non-chiral monovalent or divalent groups chosenfrom steroid radicals, terpenoid radicals, alkaloid radicals andmixtures thereof, wherein the substituents are independently chosen fromC₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl,cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is a structure having from2 to 4 reactive groups or P is an unsubstituted or substituted ringopening metathesis polymerization precursor; c) the group Q is hydroxy,amino, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy,silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,thioisocyanato, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylicester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkylaminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene, C₁-C₁₈alkyloxycarbonyloxy, or halocarbonyl; d) each L is independently chosenfor each occurrence, the same or different, from a single bond, apolysubstituted, monosubstituted, unsubstituted or branched spacerindependently chosen from aryl, (C₁-C₃₀)alkyl, (C₁-C₃₀)alkylcarbonyloxy,(C₁-C₃₀)alkylamino, (C₁-C₃₀)alkoxy, (C₁-C₃₀)perfluoroalkyl,(C₁-C₃₀)perfluoroalkoxy, (C₁-C₃₀)alkylsilyl, (C₁-C₃₀)dialkylsiloxyl,(C₁-C₃₀)alkylcarbonyl, (C₁-C₃₀)alkoxycarbonyl,(C₁-C₃₀)alkylcarbonylamino, (C₁-C₃₀)alkylaminocarbonyl,(C₁-C₃₀)alkyloxycarbonyloxy, (C₁-C₃₀)alkylaminocarbonyloxy,(C₁-C₃₀)alkylaminocarbonylamino, (C₁-C₃₀)alkylurea,(C₁-C₃₀)alkylthiocarbonylamino, (C₁-C₃₀)alkylaminocarbonylthio,(C₂-C₃₀)alkenyl, (C₁-C₃₀)thioalkyl, (C₁-C₃₀)alkylsulfonyl,(C₁-C₃₀)alkylsulfinyl, or (C₁-C₃₀)alkylsulfoyloxy wherein eachsubstituent is independently chosen from (C₁-C₁₈)alkyl, (C₁-C₁₈)alkoxy,fluoro, chloro, bromo, cyano, (C₁-C₁₈)alkanoate ester, isocyanato,thioisocyanato, or phenyl; e) the group R is selected from hydrogen,C₁-C₁₈) alkyl, C₁-C₁₈ alkoxy, C₁-C₁8 alkoxycarbonyl, C₃-C₁₀ cycloalkyl,C₃-C₁₀ cycloalkoxy, poly(C₁-C₁₈ alkoxy), or a straight-chain or branchedC₁-C₁8 alkyl group that is unsubstituted or substituted with cyano,fluoro, chloro, bromo, or C₁-C₁₈ alkoxy, or poly-substituted withfluoro, chloro, or bromo; and f) the groups Mesogen-1 and Mesogen-2 areeach independently a rigid straight rod-like liquid crystal group, arigid bent rod-like liquid crystal group, or a rigid disc-like liquidcrystal group; and where w is an integer from 1 to 26, y is an integerfrom 2 to 25, z is 1 or 2, provided that when the group X is representedby R, then w is an integer from 1 to 25, and z is 1; the group X isrepresented by-(L)_(y)-R, then w is 1, y is an integer from 2 to 25, andz is 1; the group X is represented by-(L)-R, then w is an integer from 3to 26, and z is 2; the group X is represented by -(L)_(w)-Q; then if Pis represented by the group Q, then w is 1, and z is 1; and if P isother than the group Q, then each w is independently an integer from 1to 26 and z is 1; the group X is represented by

 the w is 1, y is an integer from 2 to 25, and z is 1; the group X isrepresented by-(L)_(y)-P, then w is 1, y is an integer from 2 to 25, andz is 1 and -(L)_(y)- comprises a linear sequence of at least 25 bondsbetween the mesogen and P; and the group X is representedby-(L)_(w)-[(L)_(w)-P]_(y), then each w is independently an integer from1 to 25, y is an integer from 2 to 6, and z is
 1. 3. Thephase-separating polymer system of claim 2, wherein the groupsMesogen-1and Mesogen-2 each independently have a structure representedby:—[S¹]_(c)-[G¹ —[S²]_(d)]_(d′)-[G² —[S³]_(e)]_(e′)-[G³—[S⁴]_(f)]_(f′)—S⁵— where: (i) each G¹, G², and G³ is independentlychosen for each occurrence from: a divalent group chosen from: anunsubstituted or a substituted aromatic group, an unsubstituted or asubstituted alicyclic group, an unsubstituted or a substitutedheterocyclic group, and mixtures thereof, wherein substituents arechosen from: the group P, halogen, C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈alkylcarbonyl, C₁-C₁₈ alkyloxycarbonyloxy, aryloxycarbonyloxy,perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino, C₁-C₁₈acetyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain orbranched C₁-C₁₈ alkyl group that is mono-substituted with cyano, halo,or C₁-C₁₈ alkoxy, or poly-substituted with halo, and a group comprisingone of the following formulae: -M(T)_((t-1)) and -M(OT)_((t-1)), whereinM is chosen from aluminum, antimony, tantalum, titanium, zirconium andsilicon, T is chosen from organofunctional radicals, organofunctionalhydrocarbon radicals, aliphatic hydrocarbon radicals and aromatichydrocarbon radicals, and t is the valence of M; (ii) c, d, e, and f areeach independently chosen from an integer ranging from 0 to 20,inclusive; d′, e′ and f′ are each independently an integer from 0 to 4provided that a sum of d′+e′+f′ is at least 1; and each S¹, S², S³, S⁴,and S⁵ is independently chosen for each occurrence from a spacer unitchosen from: (A) —(CH₂)_(g)—, —(CF₂)_(h)—, —Si(CH₂)_(g)—, or—(Si(CH₃)₂O)_(h)—, wherein g is independently chosen for each occurrencefrom 1 to 20 and h is a whole number from 1 to 16 inclusive; (B) —N(Z)—,—C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)₂—C(Z′)₂—, or a single bond, wherein Z isindependently chosen for each occurrence from hydrogen, C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl and aryl, and Z′ is independently chosen for eachoccurrence from C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl; or (C) —O—,—C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—, —(O)S(O)O—, —O(O)S(O)O—orstraight-chain or branched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkyleneresidue being unsubstituted, mono-substituted by cyano or halo, orpoly-substituted by halo; provided that when two spacer units comprisingheteroatoms are linked together the spacer units are linked so thatheteroatoms are not directly linked to each other and when S₁ and S₅ arelinked to another group, they are linked so that two heteroatoms are notdirectly linked to each other.
 4. The phase-separating polymer system ofclaim 1, wherein the guest phase at least partially cures at a slowerrate than the matrix phase.
 5. The phase-separating polymer system ofclaim 1, wherein the guest phase at least partially cures by a differentpolymerization initiation method or a different polymerization mechanismthan the matrix phase.
 6. The phase-separating polymer system of claim1, wherein the at least partially cured guest phase has a lower Fischermicrohardness compared to the at least partially cured matrix phase. 7.The phase-separating polymer system of claim 1, wherein the at leastpartially cured guest phase has a higher Fischer microhardness comparedto the at least partially cured matrix phase.
 8. The phase-separatingpolymer system of claim 1, wherein the at least one photoactive materialhas faster kinetics in the guest phase than a photoactive material inthe at least partially cured matrix phase.
 9. The phase-separatingpolymer system of claim 1, wherein at least a portion of at least one ofthe at least first liquid crystal monomer of the at least partiallycured matrix phase and the at least one liquid crystal material of theguest phase is at least partially ordered.
 10. The phase-separatingpolymer system of claim 9, wherein at least a portion of the at leastfirst liquid crystal monomer of the at least partially cured matrixphase and at least a portion of the at least one liquid crystal materialof the guest phase are at least partially ordered such that the at leastpartially ordered portion of the at least first liquid crystal monomerof the at least partially cured matrix phase has a first generaldirection and the at least partially ordered portion of the at least oneliquid crystal material of the guest phase has a second generaldirection that is generally parallel to the first general direction. 11.The phase-separating polymer system of claim 1, wherein the at least onephotoactive material is adapted to switch from a first state to a secondstate in response to at least actinic radiation, and to revert back tothe first state in response to thermal energy.
 12. The phase-separatingpolymer system of claim 1, wherein at least one of the at leastpartially cured matrix phase and the guest phase further comprises oneor more additive selected from a liquid crystal, a liquid crystalcontrol additive, a non-linear optical material, a dye, a dichroic dye,an alignment promoter, a kinetic enhancer, a photoinitiator, a thermalinitiator, a surfactant, a polymerization inhibitor, a solvent, a lightstabilizer, a heat stabilizer, a mold release agent, a rheology controlagent, a leveling agent, a free radical scavenger, a coupling agent, atilt control additive, a block or non-block polymeric material, or anadhesion promoter.
 13. An article of manufacture comprising: an at leastpartially cured matrix phase comprising: a polymeric residue of at leasta first liquid crystal monomer; and a guest phase comprising: at leastone photoactive material selected from photochromic compounds andphotochromic-dichroic compounds; and a residue of at least one secondliquid crystal monomer, such that the quest phase is an at leastpartially cured guest phase, wherein at least one of the first liquidcrystal monomer of the matrix phase and the at least one second liquidcrystal monomer of the guest phase comprises at least one mesogencontaining compound having a structure represented by Formula 1:

where, a) each X is independently: i) a group R, ii) a group representedby-(L)_(y)-R, iii) a group represented by-(L)-R, iv) a group representedby-(L)_(w)-Q; v) a group represented by

vi) a group represented by-(L)_(y)-P; or vii) a group representedby-(L)_(w)-[(L)_(w)-P]_(y); b) each P is a reactive group independentlyselected from a group Q, hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈alkyl, C₁-C₁₈ alkoxy, amino(C₁-C₁₈)alkylene, C₁-C₁₈ alkylamino,di-(C₁-C₁₈)alkylamino, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈alkoxy(C₁-C₁₈)alkoxy, nitro, poly(C₁-C₁₈)alkyl ether,(C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkylene, polyethyleneoxy,polypropyleneoxy, ethylene, acryloyl, acryloyloxy(C₁-C₁₈)alkylene,methacryloyl, methacryloyloxy(C₁-C₁₈)alkylene, 2-chloroacryloyl,2-phenylacryloyl, acryloylphenylene, 2-chloroacryloylamino,2-phenylacryloylaminocarbonyl, oxetanyl, glycidyl, cyano,isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinyl ether, vinyl ester,a styrene derivative, main-chain and side-chain liquid crystal polymers,siloxane derivatives, ethyleneimine derivatives, maleic acidderivatives, fumaric acid derivatives, unsubstituted cinnamic acidderivatives, cinnamic acid derivatives that are substituted with atleast one of methyl, methoxy, cyano and halogen, or substituted orunsubstituted chiral or non-chiral monovalent or divalent groups chosenfrom steroid radicals, terpenoid radicals, alkaloid radicals andmixtures thereof, wherein the substituents are independently chosen fromC₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀ cycloalkyl, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano, cyano(C₁-C₁₈)alkyl,cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is a structure having from2 to 4 reactive groups or P is an unsubstituted or substituted ringopening metathesis polymerization precursor; c) the group Q is hydroxy,amino, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy,silyihydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,thioisocyanato, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylicester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkylaminocarbonyl, aminocarbonyl(C₁-C₁₈)alkylene, C₁-C₁₈alkyloxycarbonyloxy, or halocarbonyl; d) each L is independently chosenfor each occurrence, the same or different, from a single bond, apolysubstituted, monosubstituted, unsubstituted or branched spacerindependently chosen from aryl, (C₁-C₃₀)alkyl, (C₁-C₃₀)alkylcarbonyloxy,(C₁-C₃₀)alkylamino, (C₁-C₃₀)alkoxy, (C₁-C₃₀)perfluoroalkyl,(C₁-C₃₀)perfluoroalkoxy, (C₁-C₃₀)alkylsilyl, (C₁-C₃₀)dialkylsiloxyl,(C₁-C₃₀)alkylcarbonyl, (C₁-C₃₀)alkoxycarbonyl,(C₁-C₃₀)alkylcarbonylamino, (C₁-C₃₀)alkylaminocarbonyl,(C₁-C₃₀)alkyloxycarbonyloxy, (C₁-C₃₀)alkylaminocarbonyloxy,(C₁-C₃₀)alkylaminocarbonylamino, (C₁-C₃₀)alkylurea,(C₁-C₃₀)alkylthiocarbonylamino, (C₁-C₃₀)alkylaminocarbonylthio,(C₂-C₃₀)alkenyl, (C₁-C₃₀)thioalkyl, (C₁-C₃₀)alkylsulfonyl,(C₁-C₃₀)alkylsulfinyl, or (C₁-C₃₀)alkylsulfoyloxy wherein eachsubstituent is independently chosen from (C₁-C₁₈)alkyl, (C₁-C₁₈)alkoxy,fluoro, chloro, bromo, cyano, (C₁-C₁₈)alkanoate ester, isocyanato,thioisocyanato, or phenyl; e) the group R is selected from hydrogen,C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, C₁-C₁₈ alkoxycarbonyl, C₃-C₁₀ cycloalkyl,C₃-C₁₀ cycloalkoxy, poly(C₁-C₁₈ alkoxy), or a straight-chain or branchedC₁-C₁₈ alkyl group that is unsubstituted or substituted with cyano,fluoro, chloro, bromo, or C₁-C₁₈ alkoxy, or poly-substituted withfluoro, chloro, or bromo; and f) the groups Mesogen-1 and Mesogen-2 areeach independently a rigid straight rod-like liquid crystal group, arigid bent rod-like liquid crystal group, or a rigid disc-like liquidcrystal group; and where w is an integer from 1 to 26, y is an integerfrom 2 to 25, z is 1 or 2, provided that when: the group X isrepresented by R, then w is an integer from 1 to 25, and z is 1; thegroup X is represented by -(L)_(y)-R, then w is 1, y is an integer from2 to 25, and z is 1; the group X is represented by -(L)-R, then w is aninteger from 3 to 26, and z is 2; the group X is represented by-(L)_(w)-Q; then if P is represented by the group Q, then w is 1, and zis 1; and if P is other than the group Q, then each w is independentlyan integer from 1 to 26 and z is 1; the group X is represented by

 then w is 1, y is an integer from 2 to 25, and z is 1; the group X isrepresented by-(L)_(y)-P, then w is 1, y is an integer from 2 to 25, andz is 1 and -(L)_(y)-comprises a linear sequence of at least 25 bondsbetween the mesogen and P; and the group X is representedby-(L)_(w)-[(L)_(w)-P]_(y), then each w is independently an integer from1 to 25, y is an integer from 2 to 6, and z is 1, and wherein at least aportion of the guest phase separates from at least a portion of thematrix phase during the at least partial curing of the polymeric residueof at least the first liquid crystal monomer.
 14. A phase-separatingpolymer system comprising: an at least partially cured matrix phasecomprising: a polymeric residue of at least a first liquid crystalmonomer; and a guest phase comprising: at least one photoactive materialselected from photochromic compounds and photochromic-dichroiccompounds; and at least one liquid crystal material, wherein at least aportion of the guest phase separates from at least a portion of thematrix phase during at least partial curing of the polymeric residue ofthe at least first liquid crystal monomer, and wherein the at least onephotoactive material has faster kinetics in the guest phase than aphotoactive material in the at least partially cured matrix phase.
 15. Aphase-separating polymer system comprising: an at least partially curedmatrix phase comprising: a polymeric residue of at least a first liquidcrystal monomer; and a guest phase comprising: at least one photoactivematerial selected from photochromic compounds and photochromic-dichroiccompounds; and at least one liquid crystal material, wherein at least aportion of the guest phase separates from at least a portion of thematrix phase during at least partial curing of the polymeric residue ofthe at least first liquid crystal monomer, wherein at least a portion ofat least one of the at least first liquid crystal monomer of the atleast partially cured matrix phase and the at least one liquid crystalmaterial of the guest phase is at least partially ordered, and whereinat least a portion of the at least first liquid crystal monomer of theat least partially cured matrix phase and at least a portion of the atleast one liquid crystal material of the guest phase are at leastpartially ordered such that the at least partially ordered portion ofthe at least first liquid crystal monomer of the at least partiallycured matrix phase has a first general direction and the at leastpartially ordered portion of the at least one liquid crystal material ofthe guest phase has a second general direction that is generallyparallel to the first general direction.
 16. A phase-separating polymersystem comprising: an at least partially cured matrix phase comprising:a polymeric residue of at least a first liquid crystal monomer; and aguest phase comprising: at least one photoactive material selected fromphotochromic compounds and photochromic-dichroic compounds; and at leastone liquid crystal material, wherein at least a portion of the guestphase separates from at least a portion of the matrix phase during atleast partial curing of the polymeric residue of the at least firstliquid crystal monomer, and wherein said first liquid crystal monomer ofsaid at least partially cured matrix phase comprises at least one firstliquid crystal monomer represented by the following Formula LCM-1,

in which n has an average value of 8.1, said photoactive material ofsaid guest phase comprises3-(4-fluorophenyl-3-(4-piperazinophenyl)-13-ethyl-13-methoxy-6-methoxy-7-(4-(4-(trans)phentylcyclohexyl)benzoyloxyyphenyl)benzoyloxy-indeno[2′,3′:3,4]naphtho[1,2-b]pyran, and said liquid crystal material of saidguest phase comprises at least one liquid crystal material representedby the following Formula LCM-2,

in which n has an average value of 2.